KR101777294B1 - Polyketone composition - Google Patents
Polyketone composition Download PDFInfo
- Publication number
- KR101777294B1 KR101777294B1 KR1020160014247A KR20160014247A KR101777294B1 KR 101777294 B1 KR101777294 B1 KR 101777294B1 KR 1020160014247 A KR1020160014247 A KR 1020160014247A KR 20160014247 A KR20160014247 A KR 20160014247A KR 101777294 B1 KR101777294 B1 KR 101777294B1
- Authority
- KR
- South Korea
- Prior art keywords
- polyketone
- bis
- plasticizer
- weight
- parts
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Abstract
According to a preferred embodiment of the present invention, a polyketone resin; And a plasticizer, wherein the plasticizer is a polyketone to which an amine-substituted polyglycol is applied at a terminal thereof, and which is represented by the following chemical formula (1). The composition of the present invention is plasticized by adding a branching agent to the main chain due to the plasticizer even when the composition is applied to a continuous contact with a solvent, so that the plasticizer is not eluted and there is no change in physical properties.
(1)
(n = 1 to 100)
Description
The present invention relates to a polyketone composition, which uses a polyketone reactive plasticizer to which an amine-substituted polyglycol is applied at its terminal, so that even when applied to a product in which the solvent is continuously contacted, the plasticizer is not eluted, To a polyketone composition.
In the case where the conventional polyketone composition is used in applications where the solvent is continuously contacted, there is a possibility that the plasticizer elutes and affects the physical properties of the product.
In order to solve the above problems, it is an object of the present invention to provide a polyketone composition which is free from plasticizer elution and does not change its physical properties even when a solvent is continuously contacted with a product by using a plasticizer plasticized with a branch in the main chain thereof .
According to a preferred embodiment of the present invention, a polyketone resin; And a plasticizer, wherein the plasticizer is a polyketone to which an amine-substituted polyglycol is applied at a terminal thereof, and which is represented by the following chemical formula (1).
(1)
(n = 1 to 100)
Herein, the plasticizer is 1 to 10 parts by weight based on 100 parts by weight of polyketone.
The composition of the present invention is plasticized by adding a branching agent to the main chain due to the plasticizer even when the composition is applied to a continuous contact with a solvent, so that the plasticizer is not eluted and there is no change in physical properties.
Hereinafter, the present invention will be described in detail.
Polyketone composition
The flexible polyketone composition of the present invention is a flexible polyketone composition comprising a polyketone resin; And a plasticizer; and more specifically, the plasticizer is 1 to 10 parts by weight in 100 parts by weight of the polyketone resin.
The polyketone resin of the composition of the present invention is a new resin developed in recent years and is excellent in mechanical properties such as impact strength and molding characteristics and is a thermoplastic synthetic resin which is usefully applied to molded articles such as food containers and various parts. The mechanical properties of the polyketone resin belong to the category of high performance plastics. Polyketone resins having other desirable properties such as conductivity while retaining inherent physical properties such as mechanical properties and molding properties are widely used for various purposes. In addition, polyketone resin is a polymer material synthesized from carbon monoxide as a raw material, and has attracted great attention as an environmentally friendly material.
Generally, the polyketone resin is synthesized from carbon monoxide and olefins. For example, U.S. Patent No. 4,843,144 discloses line alternating polymers synthesized from olefins such as ethylene and propylene and carbon monoxide. The polyketone resin produced in this patent has been shown to have excellent impact resistance, high rebound resilience at room temperature and low temperature, and excellent creep properties.
In recent years, among polyketones, there is a growing interest in a series of alternating polyketones in which ketone groups and at least one ethylenically unsaturated hydrocarbon are alternately polymerized and improved in mechanical properties and molding characteristics. For example, U.S. Patent No. 4,880,903 discloses a polyketone terpolymer in which ketone groups, ethylene, and other olefinically unsaturated hydrocarbons (such as propylene) are alternately polymerized and formed.
The contents of the aforementioned U.S. Patent Nos. 4,843,144 and 4,880,903 are incorporated herein by reference.
Specifically, the linear alternating polyketone as a main component of the polyketone resin composition of the present invention is a linear alternating structure composed of a ketone group and at least one ethylenically unsaturated hydrocarbon, and substantially one carbon monoxide (or ketone group ), And is excellent in physical properties, appearance characteristics and molding properties.
The polyketone resin is a copolymer composed of repeating units represented by the general formulas (1) and (2), and it is preferable that y / x is 0.1 to 0.3. When the value of the y / x value is less than 0.1, there is a limit of low melting and workability, and when it exceeds 0.3, the mechanical properties are poor. Further, y / x is more preferably from 0.12 to 0.17.
- [- CH2CH2-CO] x- (1)
- [- CH2 --CH (CH3) - CO] y - (2)
Ethylenically unsaturated hydrocarbons suitable for use as precursors of the polyketone are, on the other hand, ethylenically unsaturated hydrocarbons suitable for use as precursors of the polyketones include ethene,? -Olefins (e.g., propene, 1-butene aliphatic hydrocarbons such as isobutene, 1-hexene and 1-octene, or aryl aliphatic hydrocarbons in which aryl substituents are formed on aliphatic molecules, in particular ethylenically unsaturated carbon Is an aryl aliphatic hydrocarbon having an aryl substituent on the atom. Examples of the aryl aliphatic hydrocarbon in the ethylenic unsaturated hydrocarbon include styrene, p-methylstyrene, p-ethylstyrene, and m-isopropyl styrene.
Such ethylenically unsaturated hydrocarbons and ketone compounds are copolymerized to form a linear alternating polyketone. Among them, a linear alternating polyketone formed by copolymerization of ethene and a ketone compound, or a mixture of at least three Linear alternating polyketone formed by copolymerization of an ethylenically unsaturated hydrocarbon having a carbon atom is preferable in view of the fact that the copolymerization reaction is easy and the molecular weight of the copolymerized linear alternating polyketone is relatively uniform. In short, the preferred polyketone resin is a copolymer of carbon monoxide and ethene, more preferably a second ethylenically unsaturated hydrocarbon having carbon monoxide, ethene and at least three carbon atoms (especially propene) is a linear terpolymer with an a-olefin.
Particularly preferred are polyketone polymers having a number average molecular weight of from 100 to 200,000, especially from 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer are determined according to the molecular weight, depending on whether the polymer is a copolymer or a terpolymer and, in the case of a terpolymer, the properties of the second hydrocarbon part. The melting point of the total of the polymers used in the present invention is 175 ° C to 300 ° C, and generally 210 ° C to 270 ° C. The intrinsic viscosity (LVN) of the polymer measured by HFIP (hexafluoroisopropyl alcohol) at 60 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, preferably 0.8 dl / g to 4 dl / g, More preferably, it is 1.0 dl / g to 1.7 dl / g. If the intrinsic viscosity is less than 1.0 dl / g, the mechanical properties are deteriorated. If the intrinsic viscosity exceeds 1.7 dl / g, the workability 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. When the ratio is less than 1.5, the polymerization yield decreases. When the ratio is more than 2.5, the moldability is poor. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst is increased or when the polymerization temperature is 100 ° C or higher, the molecular weight distribution becomes larger.
The melting point of the polyketone resin is usually in the range of 175 ° C to 300 ° C, specifically 210 ° C to 270 ° C.
On the other hand, the plasticizer to be used in the present invention is a polyglycol substituted with an amine at the terminal thereof as a reactive plasticizer of polyketone. The structure of the plasticizer used in the present invention is represented by the following general formula (1).
[Chemical Formula 1]
Wherein R is an alkyl group containing hydrogen or methane.
n is from 1 to 100;
The plasticizer preferably comprises 1 to 10 parts by weight based on 100 parts by weight of the total polyketone. If the content of the plasticizer is less than 1 part by weight, flexibility may be deteriorated. If the amount is more than 10 parts by weight, the mechanical stiffness may be deteriorated.
The polyketone resin composition of the present invention may additionally contain additives commonly used in the art within the scope not deviating from the object.
In one preferred embodiment, antioxidants, heat stabilizers, lubricants, processing aids and weathering stabilizers may be added to the polyketone resin composition of the present invention, alone or in combination.
As the antioxidant, a phenolic oxamide antioxidant may be used, which has a deactivation effect of the metal catalyst used in the polymerization. The antioxidant is preferably contained in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the polyketone resin. If the content of the antioxidant is less than 0.1 parts by weight, the deactivation function of the metal catalyst may be deteriorated. If the amount is more than 0.5 parts by weight, the physical properties of the product may be deteriorated.
Examples of the heat stabilizer include phosphorus thermal stabilizers, particularly hydroxy apatite represented by M 10 (PO 4 ) 6 (OH) 2 (wherein M is barium, strontium or calcium), preferably calcium hydroxyapatite Can be used, which suppresses the problem of an increase in viscosity during processing. The heat-resistant stabilizer is preferably contained in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the polyketone resin. If the content of the heat-resistant stabilizer is less than 0.1 parts by weight, the viscosity-increasing inhibiting function may be deteriorated. If the content is more than 2 parts by weight, the physical properties of the product may be deteriorated.
As the activator, an ethylene-methacrylic acid ester and / or a polyethylene-based synthetic lubricant such as ethylene bisstearamide, which is an acrylic lubricant, may be used. These lubricants are preferably contained in an amount of 0.1 to 1 part by weight per 100 parts by weight of the polyketone resin. If the content of the lubricant is less than 0.1 part by weight, the appearance quality may be deteriorated, and if it exceeds 1 part by weight, the mechanical properties may be deteriorated.
As the processing agent, ethylene methacrylic acid may be used. As the weather stabilizer, a benzotriazole-based material, a triazine-based material, a hindered amine-based material, or the like may be used, but not always limited thereto.
As described above, the polyketone resin composition of the present invention can be molded into a variety of products by extrusion, injection molding, or the like.
Polyketone Method for producing resin composition
According to another aspect of the present invention, there is provided a process for producing the polyketone composition of the present invention as described above.
The method for producing a polyketone composition of the present invention comprises: preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bidentate compound of phosphorus; Preparing a mixed solvent (polymerization solvent) containing an alcohol (for example, methanol) and water; Conducting the polymerization in the presence of the catalyst composition and the mixed solvent to prepare a linear terpolymer of carbon monoxide, ethylene and propylene; Removing the remaining catalyst composition from the linear terpolymer with a solvent (e.g., alcohol and acetone) to obtain a polyketone resin; And a reaction-type plasticizer to which the polyketone resin is subjected to amine-substituted polyglycol at the terminal thereof to prepare a composition.
As a method of producing the polyketone polymer, liquid phase polymerization in which carbon monoxide and olefin are carried out in an alcohol solvent through a catalyst composition composed of a palladium compound, an acid having 6 or less of PKa, and a ligand compound of phosphorus can be employed. The polymerization temperature is preferably from 50 to 100 ° C. and the reaction pressure is from 40 to 60 bar. The polymer is recovered through filtration and purification processes 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-toluenesulfonic acid, sulfuric acid, and sulfonic acid. In the present invention, trifluoroacetic acid is used and its amount is preferably 6 to 20 equivalents based on palladium. Also, 1,3-bis [di (2-methoxyphenylphosphino)] propane is preferably used as the left-handed compound of phosphorus, and the amount to be used is preferably 1 to 1.2 equivalents based on palladium.
Hereinafter, the polymerization process of the polyketone polymer will be described in detail.
The repeating unit derived from carbon monoxide, an ethylenically unsaturated compound and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, particularly repeating units derived from carbon monoxide, and ethylenically unsaturated compounds and repeating units derived from propylenically unsaturated compounds are substantially Are excellent in mechanical properties and thermal properties, excellent in processability, high in abrasion resistance, chemical resistance and gas barrier property, and are useful materials for various applications. It is considered that the high molecular weight product of the copolymerized polyketone having three or more members is more useful as an engineering plastic material having higher workability and thermal properties and having excellent economy. Particularly, it has high abrasion resistance and can be used in light gasoline tanks because of high gas barrier properties such as parts of gears of automobiles, high chemical resistance, and lining materials of chemical transport pipes. In the case of using an ultrahigh molecular weight polyketone having an intrinsic viscosity of 2 or more as the fiber, it is possible to conduct stretching at a high magnification and to have a high strength and a high modulus of elasticity oriented in the stretching direction as belts, reinforcements of rubber hoses, tire cords, And is suitable for use in building materials and industrial materials.
The production method of polyketone is carried out in the presence of an organometallic complex catalyst comprising (a) a Group 9, 10 or 11 transition metal compound, and (b) a ligand having an element of Group 15 elements, Wherein the carbon monoxide, ethylene and propylene are subjected to liquid phase polymerization in a mixed solvent of an alcohol (e.g., methanol) and water to produce a linear terpolymer, As the 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, a ketal may be formed to lower the heat stability in the process. If the amount is more than 10 parts by weight, the mechanical properties of the product may be deteriorated.
Wherein the catalyst comprises (a) a Group 9, 10 or 11 transition metal compound of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature, 1989) and (b) a ligand having an element of Group 15 elements.
Examples of the Group 9 transition metal compound in the ninth, tenth, or eleventh group transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamates, and sulfonates, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate, and ruthenium trifluoromethanesulfonate.
Examples of the Group 10 transition metal compounds include complexes of nickel or palladium, carbonates, phosphates, carbamates, sulfonates and the like. Specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, palladium trifluoroacetate , Palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium and palladium sulfate.
Examples of the Group 11 transition metal compound include copper or silver complexes, carbonates, phosphates, carbamates, and sulfonates, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, Examples of the fluoroacetic acid include silver acetyl acetate, trifluoromethanesulfonic acid and the like.
Of these, the transition metal compound (a), which is preferable inexpensively and economically, is nickel and copper compounds, and the preferable transition metal compound (a) in terms of the yield of the polyketone and the molecular weight is the palladium compound, It is most preferable to use palladium acetate.
Examples of the ligands (b) having an atom of Group XIII include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'- Bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) (2-methoxyphenyl) propane, 1,3-bis [di (2-isopropyl) Bis (diphenylphosphino) cyclohexane, 1,2-bis (diphenylphosphino) phosphine] propane, (Diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) (Diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxy- (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2- Spinosyns; there may be mentioned a ligand, such as propane.
Among these ligands, preferred ligands (b) having a Group 15 element are phosphorus ligands having an atom of Group 15, and particularly preferred ligands in terms of yield of polyketone are 1,3-bis [di (2- Methoxyphenyl) phosphino] propane and 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, Di (2-methoxyphenyl) phosphino] propane, and it is safe in that it does not require an organic solvent. Soluble sodium salts such as 1,3-bis [di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino] propane, 1,2- ] Methyl] benzene, and 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane are preferred for ease of synthesis and availability in large quantities and economically. The preferred ligand (b) having a Group 15 atom is 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis (diphenylphosphino) Bis (di (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5- -Methoxyphenyl) phosphine).
(2)
Bis (bis (2-methoxyphenyl) phosphine) bis ((2,2-dimethyl-1,3-dioxane-5,5- Activity equivalent to that of 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 The structure is simpler and has 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 of the present invention, while further reducing its manufacturing cost and cost. A method for producing a ligand for a polyketone polymerization catalyst is as follows. ((2,2-dimethyl) -2,3-dioxolane was obtained by using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) is obtained by reacting a bis (methylene) . The process for preparing a ligand for a polyketone polymerization catalyst according to the present invention is a process for producing a ligand for a polyketone polymerization catalyst which comprises reacting 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially synthesized in a large amount.
It is also preferable to use bis (bis (2-methoxyphenyl) phosphine as the ligand (cyclohexane-1,1-diylbis (methylene)) bis Respectively.
In a preferred embodiment, the process for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises: (a) introducing bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) into a reaction vessel under nitrogen atmosphere, Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the resulting mixture, followed by stirring and reacting; (c) adding methanol and stirring after completion of the reaction; (d) adding toluene and water, separating the layers, washing the oil layer with water, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue was recrystallized from methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5- diyl) bis (methylene)) bis (bis (2- methoxyphenyl) And a step of acquiring the image data.
The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) to be used varies depending on the kinds of the ethylenic and propylenically unsaturated compounds to be selected and other polymerization conditions. Therefore, But it is usually from 0.01 to 100 mmol, preferably from 0.01 to 10 mmol, per 1 liter of the reaction zone. The capacity of the reaction zone means the liquid phase capacity of the reactor. The amount of the ligand (b) to be used is not particularly limited, but is usually 0.1 to 3 mol, preferably 1 to 3 mol, per 1 mol of the transition metal compound (a).
Further, the addition of benzophenone in the polymerization of the polyketone is another characteristic. In the present invention, an effect of improving the intrinsic viscosity of the polyketone can be achieved by adding benzophenone in the polymerization of the polyketone. The molar ratio of (a) the ninth, tenth, or eleventh transition metal compound to benzophenone is 1: 5-100, preferably 1:40-60. If the molar ratio of the transition metal to the benzophenone is less than 1: 5, the effect of improving the intrinsic viscosity of the produced polyketone is unsatisfactory. If the molar ratio of the transition metal to the benzophenone exceeds 1: 100, It is not preferable because it tends to decrease
Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, -Olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclo undecene, pentacyclopentadecene, pentacyclohexadecene, Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Ethyl acrylate, and acrylates such as methyl acrylate. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, and most preferably ethylene.
Wherein the carbon monoxide and the ethylenically unsaturated compound and the propylenically unsaturated compound are copolymerized with an organometallic complex comprising a ligand (b) having an element of group 9, group 10 or group 11 transition metal compound (a) or group 15 Catalyzed, the catalyst is produced by contacting the two components. Any method may be employed as the method of contacting. That is, the solution may be prepared as a solution in which two components are premixed in a suitable solvent, or the two components may be supplied separately to the polymerization system and contacted in the polymerization system.
On the other hand, as the palladium compound constituting the catalyst composition, palladium acetate can be used, and the amount of the palladium compound used is suitably 10 -3 to 10 -1 mole.
As the acid having a pKa value of 6 or less constituting the catalyst composition, at least one selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid and sulfonic acid, preferably trifluoroacetic acid, may be used. 6 to 20 (mol) equivalents relative to the compound is appropriate.
Examples of the bidentate ligand compound constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (e.g., 1,3-bis [di (2-methoxyphenylphosphino) propane) Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane, the amount of which is 1 to 1.2 ) Equivalent.
The carbon monoxide, ethylene and propylene are liquid phase polymerized in a mixed solvent of alcohol (e.g. methanol) and water to produce a linear terpolymer. As the mixed 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, a ketal may be formed to lower the heat stability in the process. If the amount is more than 10 parts by weight, the mechanical properties of the product may be deteriorated.
The polymerization temperature is preferably in the range of 50 to 100 ° C and the reaction pressure in the range of 40 to 60 bar. The resulting polymer is recovered through filtration and purification processes after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.
In the present invention, the obtained polyketone resin is mixed with a plasticizer and then extruded by an extruder to finally obtain a polyketone composition.
Hereinafter, the present invention will be described more specifically by way of examples. However, these examples are provided only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.
Comparative Example 1
A linear terpolymer of carbon monoxide, ethylene and propylene was added to 100 parts by weight of methanol in the presence of a catalyst composition consisting of palladium acetate, anion of trifluoroacetic acid and 1,3-bis [diphenylphosphino] The polymerization was carried out in a solvent of 70 to 90 DEG C in which water was added. The melting point of the prepared terpolymer was 220 DEG C and the intrinsic viscosity (LVN) measured on 1,1,1,3,3,3-HFIP was 1.5 dl / g.
100 parts by weight of the polyketone terpolymer prepared above was charged and pelletized on an extruder at 240 ° C using a 40 mm twin screw operated at 200 rpm.
Example 1
A linear terpolymer of carbon monoxide, ethylene and propylene was added to 100 parts by weight of methanol in the presence of a catalyst composition consisting of palladium acetate, anion of trifluoroacetic acid and 1,3-bis [diphenylphosphino] The polymerization was carried out in a solvent of 70 to 90 DEG C in which water was added. The melting point of the prepared terpolymer was 220 DEG C and the intrinsic viscosity (LVN) measured on 1,1,1,3,3,3-HFIP was 1.5 dl / g. 100 parts by weight of the polyketone terpolymer prepared above and 10 parts by weight of a plasticizer composed of the following formula 1 were put into a pellet form on an extruder at a temperature of 240 DEG C using a 40 mm biaxial screw operated at 200 rpm.
[Chemical Formula 1]
In Example 1, n was 10, and R was composed of 1: 9 parts by weight of H: Me.
Example 2
The procedure of Example 1 was repeated except that the plasticizer was composed of n = 90 and R = H: Me = 19: 3.
Example 3
The plasticizer was prepared in the same manner as in Example 1, except that n was 50 and R: H: Me was 31:10 parts by weight.
Property evaluation
The pellets prepared in Examples 1 to 3 and Comparative Example 1 were prepared as specimens, and physical properties were evaluated by the following methods. The results are shown in Table 1 below.
Tensile strength: Performed according to ASTM D638.
Flexural modulus: It was conducted according to ASTM D790.
Impact strength: ASTM D256 was carried out at room temperature and at -40 占 폚.
Bursting pressure: Performed according to KS M ISO 1402.
As shown in Table 1, in the case of Examples, the impact strength was evaluated to be superior to the Comparative Example.
Claims (3)
Comprising a plasticizer,
The polyketone composition according to claim 1, wherein the plasticizer is a polyglycol substituted with an amine at the terminal.
(1)
(n = 1 to 100)
Wherein the plasticizer is 1 to 10 parts by weight based on 100 parts by weight of the polyketone.
Wherein the polyketone resin has a viscosity of 1.0 to 1.7 dl / g and a molecular weight distribution of 1.5 to 2.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160014247A KR101777294B1 (en) | 2016-02-04 | 2016-02-04 | Polyketone composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160014247A KR101777294B1 (en) | 2016-02-04 | 2016-02-04 | Polyketone composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170092949A KR20170092949A (en) | 2017-08-14 |
| KR101777294B1 true KR101777294B1 (en) | 2017-09-13 |
Family
ID=59967461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020160014247A KR101777294B1 (en) | 2016-02-04 | 2016-02-04 | Polyketone composition |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101777294B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220160225A (en) * | 2021-05-27 | 2022-12-06 | (주)나라켐 | Resin Composite Including Cellulose and Polyketone and Method for Preparation of the Same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101950100B1 (en) * | 2017-08-21 | 2019-02-19 | 최하영 | Polyketone Composition |
| KR102011908B1 (en) * | 2018-01-08 | 2019-08-20 | 효성첨단소재 주식회사 | Polyketone fiber with improved strength and its dispersion and method for preparing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000072963A (en) | 1998-02-24 | 2000-03-07 | Shell Internatl Res Maatschappij Bv | Polyketone polymer composition |
| JP2002179905A (en) | 2000-12-18 | 2002-06-26 | Nisshinbo Ind Inc | Polyketone resin composition |
-
2016
- 2016-02-04 KR KR1020160014247A patent/KR101777294B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000072963A (en) | 1998-02-24 | 2000-03-07 | Shell Internatl Res Maatschappij Bv | Polyketone polymer composition |
| JP2002179905A (en) | 2000-12-18 | 2002-06-26 | Nisshinbo Ind Inc | Polyketone resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220160225A (en) * | 2021-05-27 | 2022-12-06 | (주)나라켐 | Resin Composite Including Cellulose and Polyketone and Method for Preparation of the Same |
| KR102543297B1 (en) | 2021-05-27 | 2023-06-14 | (주)나라켐 | Resin Composite Including Cellulose and Polyketone and Method for Preparation of the Same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170092949A (en) | 2017-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101849194B1 (en) | Flexible Polyketone composition and a hose made by the same, and method of manufacturing a hose | |
| KR101777294B1 (en) | Polyketone composition | |
| KR101684890B1 (en) | Polyketone pipe holder and its manufacturing method | |
| KR101684884B1 (en) | Polyketone vehicle engine cover | |
| KR101664250B1 (en) | Polyketone blend Fuel Filler Door | |
| KR20180085847A (en) | Polyketone composition comprising thermoplastic elastomer(TPE) and polyester resin | |
| KR20160059906A (en) | Polyketone fuel tube for vehicle | |
| KR101629841B1 (en) | Cable Tie containing polyketone blend | |
| KR101664232B1 (en) | Molded article of polyketone and polyketone clip and holder | |
| KR101684883B1 (en) | Polyketone composition for vehicle oil pan | |
| KR20180079587A (en) | Polyketone composition using the compatibilizer comprising epoxide group-grafted polyketon | |
| KR101716166B1 (en) | Polyketone air conditioner stem bolt | |
| KR101716205B1 (en) | Vehicle actuator gear comprising polyketone polymer | |
| KR101705622B1 (en) | Vehicle ash tray comprising polyketone blend | |
| KR101756642B1 (en) | Vehicle window drum comprising polyketone polymer | |
| KR101734890B1 (en) | Polyketone hose connector | |
| KR101716203B1 (en) | Vehicle slide guide comprising polyketone polymer | |
| KR101716158B1 (en) | Vehicle cup holder comprising polyketone polymer | |
| KR101777293B1 (en) | Vehicle door latch housing comprising polyketone polymer | |
| KR101767898B1 (en) | Vehicle auto gear slide comprising polyketone polymer | |
| KR101675286B1 (en) | Electrical and electroni component cap comprising polyketone blend | |
| KR101664233B1 (en) | Molded article of polyketone | |
| KR101716204B1 (en) | A shaft of vehicle HAVC switch and cam comprising polyketone polymer | |
| KR101646033B1 (en) | Polyketone cable box | |
| KR101675278B1 (en) | Polyketone screw of juicer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |