KR102228495B1 - Polyketone composition improved chemical resistance, manufacturing method of the same and component including the same - Google Patents

Abstract

The present invention relates to a polyketone composition for glove transport parts with improved chemical resistance, wherein the polyketone composition comprises: a polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon; and 0.1 to 1.0 wt% of a phosphorus-based thermal stabilizer.

Description

Polyketone composition with improved chemical resistance, manufacturing method thereof, and parts for transporting gloves including the same {POLYKETONE COMPOSITION IMPROVED CHEMICAL RESISTANCE, MANUFACTURING METHOD OF THE SAME AND COMPONENT INCLUDING THE SAME}

The present invention relates to a polyketone composition having improved chemical resistance, a method for manufacturing the same, and a component for transporting gloves including the same.

Polyketone (PK) is a copolymer of carbon monoxide, ethylene, and propylene, and has high crystallinity because it is close to linear in structure. These polyketones are materials in which raw materials and polymerization process costs are inexpensive compared to general engineering plastic materials such as polyamide, polyester, and polycarbonate, and are excellent in heat resistance, chemical resistance, impact resistance, and fuel permeability. Polyketones with these characteristics are included in general-purpose high-performance plastics and have a strength comparable to that of conventional engineering plastics.

In addition, polyketone has superior chemical resistance compared to other general polymers, so it can be applied to various industrial fields that require chemical resistance, such as gloves for transportation parts exposed to chemical substances such as strong acids and strong bases, or protective equipment for chemical experiments. .

On the other hand, in the manufacture of chemical resistant gloves, since the glove is surface-treated using nitric acid or strong acid gas, a material having excellent chemical resistance is used in the case of parts for transporting gloves.

Polyamide-based materials used as conventional parts materials are relatively expensive, sensitive to moisture, and have an inconsistent physical property retention rate according to the period of use, so they must be replaced periodically.

Accordingly, in order to apply polyketone to parts for transporting gloves that require excellent chemical resistance and property retention, there is a need for technology development of a polyketone composition having improved chemical resistance without deteriorating the original physical properties.

An object of the present invention is to provide a polyketone composition having improved chemical resistance, a method for manufacturing the same, and a component for transporting gloves including the same.

Polyketone composition according to an embodiment of the present invention is a polyketone consisting of carbon monoxide and at least one olefin-based unsaturated hydrocarbon; And 0.1 to 1.0% by weight of a phosphorus-based thermal stabilizer.

At this time, the polyketone composition may further include glass fibers, in this case, based on the total weight of the polyketone composition, the polyketone 49.0 to 98.9% by weight; 0.1 to 1.0% by weight of the phosphorus-based thermal stabilizer; And 1 to 50% by weight of the glass fiber.

In addition, the melt flow index of the polyketone composition may be 4 ~ 80g / 10min.

In addition, the melt flow index of the polyketone composition may be 1.0 to 1.2 compared to the melt flow index after heat treatment at 150° C. for 30 minutes.

In addition, the polyketone composition may have a flexural strength retention rate of 80% or more after 8 weeks by immersion in a nitric acid 10% aqueous solution, and a flexural strength retention rate of 85% or more after 8 weeks by immersion in a hydrochloric acid 10% aqueous solution.

On the other hand, the component for transporting gloves according to an embodiment of the present invention includes the polyketone composition, and the flexural strength retention rate after 6 months may be 90% or more.

According to an embodiment of the present invention, the polyketone composition can provide excellent physical property retention and economical efficiency based on excellent chemical resistance. In addition, as the polyketone composition of the present invention further includes a polyketone having excellent chemical resistance and a glass fiber as a reinforcing material, it may have a more stable physical property retention rate, a sturdy durability, and an improved service life.

Accordingly, in various industries such as automobiles, electric and electronic parts, both chemical resistance and excellent properties can be widely applied as a material for parts that require a property retention rate, and in particular, can be applied as a material for parts for gloves transport.

In the present invention, various modifications can be made and various forms can be obtained, 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 describing each drawing, similar reference numerals have been used for similar elements. In the accompanying drawings, the dimensions of the structures are shown to be enlarged than actual for clarity of the present invention. Terms such as first and second may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another component. For example, without departing from the scope of the present invention, a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element. Singular expressions include plural expressions unless the context clearly indicates otherwise.

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, a film, a region, or a plate 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 in the upper part but also in the lower part.

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

A polyketone composition according to an embodiment includes a polyketone consisting of carbon monoxide and at least one olefin-based unsaturated hydrocarbon; And a phosphorus-based thermal stabilizer. In addition, the polyketone composition may further include glass fibers.

First, the polyketone of the present invention 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 containing an aryl substituent on another aliphatic molecule, in particular an aryl aliphatic containing 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 three carbon atoms with carbon monoxide and ethene, in particular 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°C, but when the molar ratio is adjusted to 47.3:2.7:50, the melting point is adjusted to 235°C.

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 generally 175°C to 300°C, and generally 210°C to 270°C. The intrinsic viscosity (IV) of the polymer measured at 60°C with HFIP (Hexafluoroisopropylalcohol) using a standard customs viscosity measuring device is 0.5 dl/g to 10 dl/g, and preferably 0.8 dl/g to 4 dl/g, and more Preferably, it is 1.2dl/g-1.4dl/g. At this time, when the number of intrinsic viscosity is less than 1.2dl/g, mechanical properties are deteriorated, and when it exceeds 1.4dl/g, processability is deteriorated.

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.

As a manufacturing method of the polyketone polymer, a liquid phase polymerization carried out in an alcohol solvent through a catalyst composition consisting of a palladium compound, an acid having a PKa of 6 or less, and a diligand compound of phosphorus may be employed. The polymerization reaction temperature is preferably 50 to 100 °C and the reaction pressure is 40 to 60 bar. The polymer is recovered through filtration and purification after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

This is preferred as palladium acetate and a palladium compound in the amount of 10 ^-3 to ^10-2 1mole preferred. Specific examples of the acid having a pKa value of 6 or less include trifluoroacetic acid, p-tolyenesulfonic acid, sulfuric acid, sulfonic acid, and the like. In the present invention, trifluoroacetic acid was used, and the amount used is preferably 6 to 20 equivalents compared to palladium. In addition, 1,3-bis[di(2-methoxyphenylphosphino)]propane is preferable as the compound of phosphorus bloccoordination, and the amount used is preferably 1 to 1.2 equivalents compared to palladium.

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, in particular, repeating units derived from carbon monoxide and ethylenically unsaturated compounds, and repeating units derived from propylene-based unsaturated compounds are substantially Polyketones with 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 with 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 having high strength and high modulus of elasticity oriented in the drawing direction, it is a reinforcing material for belts, rubber hoses, tire cords, concrete It becomes a very suitable material for building materials or industrial materials.

The polyketone production method includes carbon monoxide and carbon monoxide in a liquid medium in the presence of an organometallic complex catalyst consisting of (a) a group 9, group 10, or group 11 transition metal compound, and (b) a ligand having an element of group 15. In the method of producing a polyketone by ternary copolymerization of ethylenic and propylene unsaturated compounds, the carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (e.g., methanol) and water to produce a linear terpolymer, the mixing As a solvent, a mixture of 100 parts by weight of methanol 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, the ketal is formed and heat resistance 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 9 transition metal compound among the Group 9, 10, or 11 transition metal compounds (a) include cobalt or ruthenium complexes, carbohydrates, phosphates, carbamates, sulfonates, and the like, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate, ruthenium trifluoromethane sulfonate, and the like.

Examples of the Group 10 transition metal compound include a complex of nickel or palladium, a carbonate, a phosphate, a carbamate, a sulfonic acid salt, etc., and specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, palladium trifluoroacetate. , Palladium acetylacetate, palladium chloride, bis(N,N-diethylcarbamate)bis(diethylamine)palladium, palladium sulfate, and the like.

Examples of the Group 11 transition metal compound include a complex of copper or silver, a carbonate, a phosphate, a carbamate, a sulfonic acid salt, etc., and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, silver acetate, tri Silver fluoroacetic acid, silver acetylacetate, silver trifluoromethane sulfonic acid, etc. are mentioned.

Among these, inexpensive and economically preferable transition metal compounds (a) are nickel and copper compounds, and preferable transition metal compounds (a) in terms of the yield and molecular weight of polyketones are palladium compounds, and in terms of improving catalytic activity and intrinsic viscosity. It is most preferable to use palladium acetate.

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 polyketones 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[ Di(2-methoxyphenyl)phosphino]propane, 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane, and in terms of safety without needing an organic solvent 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 have 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- Methoxyphenyl)phosphine) can be commercially synthesized in large quantities.

Meanwhile, it is also preferable to use (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine as a ligand used in the polymerization catalyst. It is the same as the reaction equation.

[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 then reacted under tosyl chloride and pyridine to obtain release. This ligand can be obtained by reacting it with 2-methoxyphenylphosphine, sodium hydride and dimethyl sulfoxide, 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 (a) adding bis(2-methoxyphenyl)phosphine and dimethylsulfoxide (DMSO) to a reaction vessel under nitrogen atmosphere and hydrogenating at room temperature. Stirring after adding sodium; (b) adding 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and dimethyl sulfoxide to the obtained mixture, followed by stirring to react; (c) adding methanol and stirring after completion of the reaction; (d) 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 (e) the residue was recrystallized under methanol ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) It can be carried out through the step of obtaining.

The amount of the transition metal compound (a) used in the Group 9, 10 or 11 transition metal compound (a) varies depending on the type of ethylenic and propylene unsaturated compound selected or other polymerization conditions. Although it cannot be limited, it is usually 0.01 to 100 millimoles, preferably 0.01 to 10 millimoles per 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) used is also not particularly limited, but it is usually 0.1 to 3 moles, preferably 1 to 3 moles, per 1 mole of the transition metal compound (a).

In addition, it is another feature that benzophenone is added during polymerization of the polyketone. In the present invention, the intrinsic viscosity of the polyketone can be improved by adding benzophenone during polymerization of the polyketone. The molar ratio of the (a) Group 9, Group 10, or Group 11 transition metal compound to benzophenone is 1:5 to 100, preferably 1:40 to 60. If the molar ratio of the transition metal and benzophenone is less than 1:5, the effect of improving the intrinsic viscosity of the prepared polyketone is not satisfactory, and if the molar ratio of the transition metal and benzophenone exceeds 1:100, the catalytic activity of the polyketone produced is rather It is not desirable because it tends to decrease.

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; And acrylic acid esters such as ethyl acrylate and methyl acrylate. 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 an organometallic complex consisting of the group 9, 10 or 11 transition metal compound (a) and a ligand having an element of group 15 (b) It is caused by a catalyst, and the catalyst is produced by contacting the two components. As a method of contacting, any method can be adopted. 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, a gas phase polymerization method in which a small amount of a polymer is impregnated with a high concentration catalyst solution, and the like 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.

Alternating linear polyketones are formed by the polymerization method as described above.

The content of the polyketone may be a residual amount such that the total weight of the polyketone composition is 100% by weight.

In addition, in the polyketone composition according to the present invention, a thermal stabilizer may be added to improve thermal stability, and a phosphorus-based thermal stabilizer is preferably used as the thermal stabilizer.

The heat stabilizer of the present invention may be 0.1 to 1.0% by weight based on the total weight of the composition, preferably 0.3 to 0.8% by weight, and more preferably 0.4 to 0.7% by weight. Here, if the thermal stabilizer is less than 0.1% by weight, the thermal stability is lowered, and it is difficult to obtain the effect of reducing the physical properties of the molded part and the effect of improving the processing stability. If it exceeds 1.0% by weight, the thermal stability is excellent, but the price increases, due to excessive input. This may cause a problem of lowering the mechanical strength.

As the type of phosphorus-based heat stabilizer specifically used, phosphate, phosphonate, phosphinate, phosphine oxide, and phosphazene may be used.

On the other hand, in the present invention, it is preferable to use a phosphate-based phosphorus-based thermal stabilizer. Tricalcium phosphate may be used as an example of such a phosphate-based thermal stabilizer. Tricalcium phosphate plays a role in maintaining the viscosity of the polyketone.

Specifically, since polyketone has a disadvantage of increasing the viscosity and gelling at high temperature, tricalcium phosphate is added to maintain the viscosity of the polyketone. Due to the addition of tricalcium phosphate, it is possible to obtain the effect of uniformly maintaining the viscosity of the polyketone, thereby minimizing damage to molded parts and maintaining low specific gravity.

In addition, the polyketone composition according to the present invention may further include glass fibers and may reinforce the mechanical properties of the composition.

At this time, based on the total weight of the polyketone composition, the content of the polyketone is 49.0 ~ 98.9% by weight; The content of the phosphorus-based thermal stabilizer is 0.1 to 1.0% by weight; The content of the glass fiber may be 1 to 50% by weight.

Preferably, the content of the polyketone may be 49.0 to 94.0% by weight. When the content of polyketone is less than 49% by weight, mechanical properties, thermal stability, and fluidity may be reduced, and when it exceeds 94% by weight, the content of specific substances added to the composition is relatively small, so that the effect of improving the property retention rate is relatively small. It can be insignificant.

In addition, the content of the glass fiber may be 1 to 50% by weight, preferably 10 to 40% by weight, more preferably 10 to 30% by weight based on the total weight of the composition. If the content of glass fiber is less than 1% by weight, the flexural modulus of the molded part is lowered and deformation may occur during use. If it exceeds 50% by weight, the melt flow index of the composition is very low, resulting in lower processability, resulting in product molding manufacturing. Difficulty arises.

In addition, the length of the glass fiber is preferably 2 to 10 mm, and may preferably be 2 to 8 mm. If the length of the glass fiber is less than 2mm, the degree of orientation of the polymer is low, and the improvement rate of mechanical properties is inefficient compared to the amount used.If it exceeds 10mm, it is difficult to quantitatively input into the twin-screw extruder during pellet production, resulting in uneven product properties. have.

On the other hand, the polyketone composition of the present invention may additionally contain conventionally known additional additives, such as antioxidants, heat stabilizers, lubricants, fillers, refractory materials, release agents, colorants, and other materials in order to improve the processability or physical properties of the polymer. I can. The content of these additional additives may be 0 to 2% by weight based on the total weight of the polyketone composition.

This polyketone composition may have a melt flow index of 4 to 80g/10min, preferably 10 to 80g/10min, and more preferably 20 to 70g/10min.

According to an embodiment of the present invention, when the melt flow index of the composition is less than 4g/10min, the viscosity of the molten resin is too high, so it may be difficult to manufacture a part through an injection machine, and when it exceeds 80g/10min, the melted resin may be difficult to manufacture. The viscosity of the resin is too low, which can increase the defect rate of the product, such as non-uniformity in weighing during part molding manufacturing.

In addition, the melt flow index of the polyketone composition according to the present invention may be 1.0 to 1.2 compared to the melt flow index after heat treatment at 150° C. for 30 minutes. As the melt flow index is maintained at a certain level even after heat treatment of the composition, there is an advantage of excellent processability and easy part molding manufacturing, and even after exposure to chemical substances, a more stable and excellent property retention rate can be provided. On the other hand, when the melt flow index of the composition is greater than 1.2 compared to the melt flow index after heat treatment, the workability is deteriorated, making it difficult to manufacture a part molding, and chemical resistance may be deteriorated.

On the other hand, the manufacturing method of the polyketone composition of the present invention is as follows.

The method for preparing a polyketone composition of the present invention comprises the steps of preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a di ligand compound of phosphorus; Preparing a mixed solvent (polymerization solvent) containing alcohol (eg, methanol) and water; Polymerizing in the presence of the catalyst composition and a mixed solvent to prepare a linear terpolymer of carbon monoxide, ethylene and propylene; Removing the catalyst composition remaining from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone resin; Dry blending the polyketone and the phosphorus-based thermal stabilizer, and then injecting it into a main feeder; Injecting the glass fiber into the side feeder; And melt-extruding with a twin-screw extruder to pelletize.

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 a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used as the mixed solvent. If the content of water in the mixed solvent is less than 2 parts by weight, the ketal is formed, and heat resistance may decrease during the process, and if it exceeds 10 parts by weight, the mechanical properties of the product may decrease.

In addition, during the polymerization, the reaction temperature is 50 ~ 100 ℃, the reaction pressure is suitable in the range of 40 ~ 60bar. The resulting polymer is recovered through filtration and purification after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

At this time, the extrusion temperature is 230 ~ 260 ℃, the screw rotation speed is preferably in the range of 100 ~ 300rpm. If the extrusion temperature is less than 230°C, kneading may not occur properly, and if it exceeds 260°C, problems related to heat resistance of the resin may occur. In addition, if the screw rotation speed is less than 100 rpm, smooth kneading may not occur, and if it exceeds 300 rpm, mechanical properties may be deteriorated.

The polyketone composition prepared as described above has a flexural strength retention rate of 80% or more after 8 weeks by immersion in a nitric acid 10% aqueous solution, and a flexural strength retention rate of 85% or more after 8 weeks by immersion in a 10% hydrochloric acid aqueous solution. The retention rate of physical properties can be improved.

Accordingly, in various industries such as automobiles, electric and electronic parts, both chemical resistance and excellent properties can be widely applied as a material for parts that require a property retention rate, and in particular, can be applied as a material for parts for gloves transport. The parts for transporting gloves are not limited depending on the part, such as a former, a holder, and an arm, and can be applied to any parts for transporting gloves that can be made of a polymer material.

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

[Example 1]

The linearly alternating polyketones consisting of carbon monoxide, ethylene and propene are palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis( It was prepared in the presence of a catalyst composition produced from 2-methoxyphenyl)phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first step of the polymerization temperature of 80°C and the second step of 84°C are performed. In the polyketone prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. In addition, the polyketone had a melting point of 220° C. and a viscosity (I.V) of 1.4 dl/g measured at 25° C. with HFIP (hexa-fluoroisopropano).

After dry-blending 99.5% by weight of the prepared polyketone and 0.5% by weight of the heat stabilizer Tricalcium phosphate, it was put into a main feeder and melt-extruded with a twin screw extruder to obtain pelletized resin pellets. At this time, the conditions of the twin-screw extruder were set by sequentially raising the input amount 40kg/hr, the screw speed 250rpm, and the temperature from 220°C to 230°C.

[Example 2]

After dry-blending 69.5% by weight of the polyketone prepared in Example 1 and 0.5% by weight of tricalcium phosphate as a heat stabilizer, it was added to the main feeder, and 30% by weight of the glass fiber was added to the side feeder. Then, it melt-extruded with a twin-screw extruder to obtain pelletized resin pellets. At this time, the conditions of the twin-screw extruder were set by sequentially raising the input amount 40kg/hr, the screw speed 250rpm, and the temperature from 220°C to 230°C.

[Example 3]

The linearly alternating polyketones consisting of carbon monoxide, ethylene and propene are palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis( It was prepared in the presence of a catalyst composition produced from 2-methoxyphenyl)phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first step of the polymerization temperature of 78°C and the second step of 84°C are performed. In the polyketone prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. In addition, the polyketone had a melting point of 220° C. and a viscosity (I.V) of 1.4 dl/g measured at 25° C. with HFIP (hexa-fluoroisopropano).

After dry-blending 89.5% by weight of the prepared polyketone and 0.5% by weight of tricalcium phosphate as a heat stabilizer, it was added to the main feeder, and 10% by weight of glass fiber was added to the side feeder, and then used as a twin-screw extruder. Melt extrusion was performed to obtain pelletized resin pellets. At this time, the conditions of the twin-screw extruder were set by sequentially raising the input amount 40kg/hr, the screw speed 250rpm, and the temperature from 220°C to 230°C.

[Comparative Example 1]

Pellets were prepared in the same manner as in Example 1, except that 100% by weight of polyketone having an intrinsic viscosity of 1.1 dl/g was used, but was prepared in the same manner as in Example 1.

[Comparative Example 2]

Pellets were prepared in the same manner as in Example 2, except that 70% by weight of polyphthalamide and 30% by weight of glass fiber were used instead of polyketone.

[Experimental Example]

The physical properties of the pellets prepared in Examples and Comparative Examples were evaluated using the following method, and the results are shown in Table 1 below.

(1) Evaluation of the chemical resistance of the composition

In order to test the chemical resistance of the prepared pellets, a specimen for measuring the flexural properties of ISO178 standard was prepared at 240°C with an injection machine with an 80 ton clamping force, and this was immersed in a 10% aqueous solution of nitric acid and a 10% hydrochloric acid solution at 50°C for 8 weeks. After confirming the retention rate of the flexural strength. At this time, the flexural strength was carried out according to ISO 178.

(2) the melt flow index of the composition

The melt flow index of the prepared pellets and the pellets were heat-treated at 150° C. for 30 minutes, and then the melt flow index was measured, and the melt flow index change was calculated by the following equation. At this time, the melt flow index was measured according to ISO 1133 at 240° C. and 2.16 kg load condition.

MFI'' = MFI/MFI' (MFI is the melt flow index before heat treatment of the pellet, MFI' is the melt flow index after heat treatment of the pellet)

(3) Retention rate of physical properties of parts for transporting gloves

The manufactured pellets were used in an injection machine with a clamping force of 440 tons to make a holder among the parts for transporting gloves and applied it to the actual process.After 6 months, the parts were recovered and cut into a size of 10 Х70 mm, and the flexural properties were measured according to ISO178 standards. The retention rate of the flexural strength was measured.

exam Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 MFI'' 1.02 1.03 1.06 1.28 0.91 nitric acid
Specimen immersion Flexural strength
Retention rate (%) 93% 83% 84% 79% 52% Hydrochloric acid specimen immersion Flexural strength
Retention rate (%) 89% 86% 88% 82% 56% Sealed parts cutting specimen Flexural strength
Retention rate (%) 107% 109% 106% Not available (variant) 88%

Referring to Table 1, it can be seen that the composition according to the embodiment contains a phosphorus-based thermal stabilizer or glass fiber, and thus has excellent chemical resistance and physical property retention. In addition, it was confirmed that the melt flow index of the polyketone composition is 1.0 to 1.2 compared to the melt flow index after heat treatment at 150° C. for 30 minutes, and the melt flow index is maintained at a certain level even after the heat treatment. As the composition according to the embodiment exhibits such a melt flow index, it can be seen that the flexural strength retention rate is 80% or more even after exposure to chemical substances such as nitric acid and hydrochloric acid. In particular, it can be seen that even in the case of the cut specimen of the sealed part, the retention rate of the flexural strength is very superior compared to the comparative example.

On the other hand, in the case of the comparative example, as the melt flow index was less than 1.0 or greater than 1.2 compared to the melt flow index after heat treatment at 150°C for 30 minutes, it was found that the flexural strength retention rate for the chemical substance was significantly lowered compared to the example. have.

As a result, since the polyketone composition prepared according to the Example exhibits superior chemical resistance and property retention than that of the comparative example, it is applied as a part for transfer of toys that requires both chemical resistance and property retention, especially as a former, a holder, an arm, etc. It is possible.

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 relevant technical field will not depart from the spirit and scope of the present invention described in the claims to be described later. It will be appreciated 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 contents described in the detailed description of the specification, but should be determined by the claims.

Claims (8)

Polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon; And
Including a polyketone composition containing 0.1 to 10% by weight of a phosphorus-based thermal stabilizer,
A component for transporting gloves with improved chemical resistance with a flexural strength retention of more than 90% after 6 months. The method of claim 1,
The polyketone composition is a component for transporting gloves with improved chemical resistance further comprising a glass fiber. The method of claim 2,
Based on the total weight of the polyketone composition, the polyketone 49.0 to 98.9% by weight; 0.1 to 1.0% by weight of the phosphorus-based thermal stabilizer; And a part for transporting gloves with improved chemical resistance comprising 1 to 50% by weight of the glass fiber. The method according to claim 1 or 2,
The melt flow index of the polyketone composition is 4 ~ 80g / 10min Chemical resistance improved gloves for transportation parts. The method according to claim 1 or 2,
The melt flow index of the polyketone composition is 1.0 to 1.2 compared to the melt flow index after heat treatment at 150°C for 30 minutes. The method according to claim 1 or 2,
A part for glove transfer with improved chemical resistance with a flexural strength retention rate of 80% or more after 8 weeks by immersion in a 10% nitric acid aqueous solution and a flexural strength retention rate of 85% or more after 8 weeks by immersion in a 10% hydrochloric acid aqueous solution. delete The method of claim 1,
The part is a part for transporting gloves with improved chemical resistance, which is one selected from a former, a holder, and an arm.