KR101807612B1 - Polyketone refrigerator door closure - Google Patents
Polyketone refrigerator door closure Download PDFInfo
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- KR101807612B1 KR101807612B1 KR1020150074034A KR20150074034A KR101807612B1 KR 101807612 B1 KR101807612 B1 KR 101807612B1 KR 1020150074034 A KR1020150074034 A KR 1020150074034A KR 20150074034 A KR20150074034 A KR 20150074034A KR 101807612 B1 KR101807612 B1 KR 101807612B1
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- refrigerator door
- door closure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
-
- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D23/00—General constructional features
- F25D23/02—Doors; Covers
- F25D23/028—Details
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/62—Mechanical aspects
Abstract
The present invention relates to a polyketone refrigerator door closure, and more particularly, to a polyketone refrigerator door closure having superior abrasion resistance using a linear alternating polyketone terpolymer.
Description
The present invention relates to a polyketone refrigerator door closer, and more particularly, to a polyketone refrigerator door closer which can be applied to refrigerator door closures as engineering plastics and has excellent abrasion resistance.
Generally, a door closer is provided on a door of a hinged shape, and functions to smoothly open and close the door when the door is opened and closed.
A typical form of such a door closure is such that the door body is provided with a closure body and the door frame or wall body body arm assembly is provided.
Generally, polyoxymethylene (hereinafter referred to as " POM ") is used as a material of the door closure. The POM itself satisfies some degree of mechanical properties and abrasion resistance. However, there is a problem that the door closure part is damaged when driven under a high load, and the crystallization degree is higher than that of other engineering plastics and the shrinkage ratio is large. It may cause noise due to the problem of dimension. Accordingly, it has become necessary to improve rigidity, abrasion resistance, and shrinkage characteristics. In addition, polyoxymethylene, which is a conventional material, has a problem that wear resistance and noise generation are limited.
On the other hand, Polyketone (PK) is an inexpensive material of raw material and polymerization process ratio compared with general engineering plastic materials such as polyamide, polyester and polycarbonate. It has excellent properties such as heat resistance, chemical resistance, fuel permeability and abrasion resistance It is widely applied to various industries.
For this reason, there is a growing interest in a family of linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, known as polyketones or polyketone polymers. U.S. Patent No. 4,880,903 discloses a linear alternating polyketone terpolymer consisting of carbon monoxide, ethylene and terephthalic unsaturated hydrocarbons such as propylene. The process for preparing the polyketone polymer is generally carried out by reacting a compound of a Group VIII metal selected from among palladium, cobalt or nickel with an anion of a strong halogen-hydrohalogentic acid, , Phosphorus, arsenic, or antimony (Antimon). U.S. Patent No. 4,843,144 discloses a process for producing a polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of a non-hydrohalogenic acid having a pKa of less than 6, and a catalyst that is a bidentate ligand .
Accordingly, the inventors of the present invention have invented a door closure made of a polyketone composition, which is a material having sufficient wear resistance and little noise generation, which is a property required for a door closer.
An object of the present invention is to provide a polyketone refrigerator door closure excellent in abrasion resistance.
In order to achieve the above object, according to a preferred embodiment of the present invention, there is provided a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2) A polyketone refrigerator door closure characterized by being manufactured by injection molding a polyketone composition containing a ketone.
- [- CH2CH2-CO] x- (1)
- [- CH2 --CH (CH3) - CO] y - (2)
(x and y represent mol% of each of the general formulas (1) and (2) in the polymer).
At this time, the polyketone composition preferably further comprises a polytetrafluoroethylene resin or a thermoplastic polyurethane resin.
The refrigerator door closer according to the present invention is characterized in that the abrasion resistance is 0.015 g or less in the base state.
In addition, the present invention is characterized in that the intrinsic viscosity of the polyketone is 1.0 to 2.0 dl / g, and the ligand of the catalyst composition used in the polyketone polymerization is ((2,2-dimethyl-1,3-dioxane-5,5 Bis (methylene)) bis (bis (2-methoxyphenyl) phosphine). The present invention also provides a polyketone refrigerator door closure.
The polyketone refrigerator door closure of the present invention can produce a polyketone refrigerator door closure excellent in abrasion resistance as compared with polyoxymethylene (POM) used in the past.
Hereinafter, the present invention will be described in detail.
The polyketone refrigerator door closure of the present invention is made of polyketone.
At this time, the polyketone refrigerator door closure of the present invention is a polyketone; And a polyketone composition comprising a polytetrafluoroethylene resin or a thermoplastic polyurethane resin, but the present invention is not limited thereto.
1. Polymerization of polyketones
Hereinafter, the polymerization method of the polyketone used in the present invention will be described in detail.
One or more olefinically unsaturated compounds (simply referred to as " A "), wherein the monomer units are alternating, and thus the polymer is composed of units of the formula - (CO) -A'- wherein A 'represents the monomer units derived from the applied monomer A ) And a high molecular weight linear polymer of carbon monoxide can be prepared by contacting monomers with a solution of a palladium-containing catalyst composition in a dilute solution in which the polymer does not dissolve or actually dissolve. During the polymerization process, the polymer is obtained in the form of a suspension in a diluent. The polymer preparation is carried out primarily batchwise.
The batchwise preparation of the polymer is typically carried out by introducing the catalyst into a reactor containing the diluent and the monomer and having the desired temperature and pressure. As the polymerization proceeds, the pressure drops, the concentration of the polymer in the diluent increases, and the viscosity of the suspension increases. The polymerization is continued until the viscosity of the suspension reaches a high value, for example, to the point where difficulties associated with heat removal occur. During batch polymer preparation, monomers can be added to the reactor during polymerization, if desired, to maintain the temperature as well as the pressure constant.
In the present invention, not only methanol, dichloromethane or nitromethane, which has been conventionally used for producing polyketones, but also mixed solvents comprising acetic acid and water, ethanol, propanol, and isopropanol can be used as the liquid medium. Particularly, when a mixed solvent of acetic acid and water is used as a liquid medium in the production of polyketone, the catalyst activity can be improved while reducing the production cost of polyketone. Further, since the use of methanol or a dichloromethane solvent forms a mechanism for causing a stopping reaction during the polymerization step, the use of acetic acid or water other than methanol or dichloromethane in the solvent does not have an effect of stopping the catalytic activity stochastically, It plays a big role in improvement.
When a mixed solvent of acetic acid and water is used as a liquid medium, when the concentration of water is less than 10% by volume, the activity is less affected by the catalytic activity, but when the concentration is 10% by volume or more, the catalytic activity increases sharply. On the other hand, when the concentration of water exceeds 30% by volume, the catalytic activity tends to decrease. In the present invention, it is preferable to use a mixed solvent comprising 70 to 90% by volume of acetic acid and 30 to 10% by volume of water as the liquid medium.
In the present invention, the organometallic complex catalyst comprises (a) a Group 9, Group 10 or Group 11 transition metal compound of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989), (b) And (c) an anion of an acid having a pKa of 4 or less.
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, and sulfonates. Specific examples thereof include nickel acetate, nickel acetyl acetate, 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 a complex of copper and silver, a carbonate, a phosphate, a carbamate, and a sulfonate, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, Examples of the trifluoroacetic acid include silver acetyl acetate, trifluoromethanesulfonic acid and the like.
Of these, transition metal compounds (a), which are inexpensive and economically preferable, are nickel and copper compounds, and preferable transition metal compounds (a) in terms of yield and molecular weight of polyketones are palladium compounds, 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).
[Chemical Formula 1]
Bis (bis (2-methoxyphenyl) phosphine) bis ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis 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.
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) varies depending on the kind of the ethylenically unsaturated compound to be selected and other polymerization conditions. But is usually 0.01 to 100 mmol, preferably 0.01 to 10 mmol, per liter of the reaction volume of the reaction zone. The capacity of the reaction zone means the liquid phase capacity of the reactor.
Examples of the anion (c) of the acid having a pKa of 4 or less include an anion of an organic acid having a pKa of 4 or less, such as trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, or m-toluenesulfonic acid; Anions of inorganic acids having a pKa of 4 or less such as perchloric acid, sulfuric acid, nitric acid, phosphoric acid, heteropoly acid, tetrafluoroboric acid, hexafluorophosphoric acid, and fluorosilicic acid; And anions of boron compounds such as trispentafluorophenylborane, trisphenylcarbenium tetrakis (pentafluorophenyl) borate, and N, N-dimethylarinium tetrakis (pentafluorophenyl) borate.
Particularly, the anion (c) of the acid having a pKa of 4 or less, which is preferable in the present invention, is p-toluenesulfonic acid, which has high catalytic activity when used with a mixed solvent of acetic acid and water as a liquid medium, It becomes possible to produce a polyketone having a high intrinsic viscosity suitable for the polyolefin.
The molar ratio of (a) the ninth, tenth or eleventh group transition metal compound and (b) the ligand having an element of Group 15 element is 0.1 to 20 moles of the Group 15 element of the ligand per 1 mole of the palladium element, Is preferably added in a proportion of 0.1 to 10 moles, more preferably 0.1 to 5 moles. When the ligand is added in an amount of less than 0.1 mole based on the palladium element, the binding force between the ligand and the transition metal decreases, accelerating the desorption of the palladium during the reaction, and causing the reaction to terminate quickly. When the ligand exceeds 20 moles When added, the ligand is shielded from the polymerization reaction by the organometallic complex catalyst, so that the reaction rate is remarkably lowered.
The molar ratio of (a) the anion of the ninth, tenth or eleventh group transition metal compound and (c) the anion of the acid having a pKa of 4 or less is 0.1 to 20 mol, preferably 0.1 to 10 mol, Mol, and more preferably 0.1 to 5 mol. When the acid is added in an amount of less than 0.1 mol based on the palladium element, the effect of improving the intrinsic viscosity of the polyketone is unsatisfactory. If the acid is added in an amount exceeding 20 mol based on the palladium element, the catalytic activity for producing the polyketone tends to be rather reduced. not.
In the present invention, the reaction gas to be reacted with the catalyst for producing polyketone is preferably a mixture of carbon monoxide and an ethylenically unsaturated compound.
Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide in the present invention include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, - C2 to C20 alpha-olefins including tetradecene, 1-hexadecene, vinylcyclohexane; Styrene, C2-C20 alkenyl aromatic compounds including? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclo undecene, pentacyclopentadecene, pentacyclohexadecene, C4 to C40 cyclic olefins including cyclododecene; C2 to C10 halogenated vinyls containing vinyl chloride; Ethyl acrylate, methyl acrylate, and mixtures of two or more selected from among C3 to C30 acrylic esters. These ethylenically unsaturated compounds are used singly or as a mixture of plural kinds. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, and most preferably ethylene.
In the production of polyketones, the charging ratio of the carbon monoxide and the ethylenic unsaturated compound is generally 1: 1. In the present invention, the charging ratio of the carbon monoxide and the ethylenic unsaturated compound is adjusted to a molar ratio of 1:10 to 10: 1 . As in the present invention, when an ethylenically unsaturated compound and carbon monoxide are mixed in an appropriate ratio, they are effective also in terms of catalytic activity, and the intrinsic viscosity improvement effect of the produced polyketone can be simultaneously achieved. When carbon monoxide or ethylene is added in an amount of less than 10 mol% or more than 90 mol%, the reactivity is poor and the physical properties of the produced polyketone may deteriorate.
A preferred process for producing a polyketone polymer is disclosed in U.S. Patent No. 4,843,144. In the present invention, a mixed solvent of acetic acid and water is used as a liquid medium, and the polymerization reaction is caused by a catalyst composition composed of (a) a palladium compound, (b) a bidentate ligand and (c) an anion of an acid having a pKa of 4 or less , The catalyst is produced by contacting the three components. Any method may be employed. A solution prepared by preliminarily mixing three components in a suitable solvent may be used, or the three components may be supplied to the polymerization system and contacted in the polymerization system.
In carrying out the present invention, the polymerization method includes a solution polymerization method using a liquid medium, a suspension polymerization method, a vapor phase polymerization method in which a small amount of a polymer is impregnated with a high concentration catalyst solution, and the like. The polymerization may be either batchwise or continuous. The reactor used in the polymerization can be used as it is or in a known manner. The polymerization temperature is not particularly limited and generally 40 占 폚 to 250 占 폚, preferably 50 占 폚 to 180 占 폚 is employed. If the reaction temperature is less than 40 ° C, the polymerization reaction is poor and the reaction does not proceed. If the reaction temperature exceeds 250 ° C, a side reaction such as oligomerization or monomer preparation and decomposition reaction is more active than polymerization reaction with a polymer, . The pressure at the time of polymerization is not particularly limited, but is generally from normal pressure to 20 MPa, preferably from 4 to 15 MPa. The polymerization reaction rate is very low at a pressure lower than the atmospheric pressure, and the side reaction speed is increased at a pressure of 20 MPa or higher.
A linear alternating polyketone is prepared by the polymerization method as described above.
2. Polyketone resin
The polyketone 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 various molded articles and parts. The mechanical properties of the polyketone resin belong to the category of high performance plastics, and they are attracting much attention as eco-friendly materials because they are polymeric materials synthesized from carbon monoxide as a raw material.
The polyketone resin is less hygroscopic than nylon, and it is possible to design various products with less changes in dimensions and physical properties due to moisture absorption. Especially, polyketone resin is more suitable for weight reduction because it has lower density than aluminum material.
On the other hand, the polyketone polymer of the present invention is a line-by-line alternating structure and substantially contains carbon monoxide per one 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. Ethylenically unsaturated hydrocarbons can also be selected from the group consisting of ethene and alpha-olefins such as propene, 1-butene, iso-butene, 1- hexene, 1- octene, , Or an aryl aliphatic group containing an aryl substituent on another aliphatic molecule, particularly containing an aryl substituent on an ethylenically unsaturated carbon atom. Examples of aryl aliphatic hydrocarbons in 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 carbon monoxide, ethene and at least three carbon atoms, in particular alpha-olefins such as propene Is a terpolymer.
When the polyketone terpolymer is used as the main polymer component of the blend of the present invention, there are at least two units containing an ethylene moiety in each unit containing the second hydrocarbon moiety in the terpolymer. It is preferable that the number of units containing the second hydrocarbon moiety is from 10 to 100.
In one embodiment, the polyketone polymer may include a unit represented by the following formula (2) as a repeating unit.
(2)
- {- CO- (- CH2 --CH2 -) -} x- {CO- (G)
In the above formula (2), G is an ethylenically unsaturated hydrocarbon, particularly an ethylenically unsaturated hydrocarbon having at least three carbon atoms, and x: y is at least 1: 0.01.
In another embodiment, the polyketone polymer is a copolymer comprising repeating units represented by the following general formulas (1) and (2), and y / x is preferably 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)
On the other hand, the polyketone resin preferably has an intrinsic viscosity (LVN) of 0.5 to 10 dl / g, more preferably 0.8 to 4 dl / g, and most preferably 1 to 2 dl / g. If the intrinsic viscosity of the polyketone resin is less than 0.5 dl / g, the mechanical properties may be deteriorated. If the intrinsic viscosity exceeds 10 dl / g, the workability may be deteriorated.
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.
On the other hand, the polyketone of the present invention as described above is molded by a method such as extrusion, injection molding or the like to be made into a polyketone refrigerator door closure.
In particular, the polyketone refrigerator door closure of the present invention has excellent mechanical strength and excellent dimensional stability.
3. Manufacturing Method
Hereinafter, a method for manufacturing the above-described polyketone refrigerator door closure will be described.
A method for producing a polyketone refrigerator door closure according to the present invention comprises the steps of: preparing a catalyst composition comprising an acid having a pKa value of a palladium compound of 6 or less and a bidentate compound of phosphorus; Preparing a mixed solvent (polymerization solvent) containing acetic acid 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 mixing and extruding the polyketone resin.
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.
As the 2-position ligand compound constituting the catalyst composition, bis (2, 2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) bis (bis (2-methoxyphenyl) ), And the amount thereof to be used is suitably 1 to 1.2 (molar) equivalent based on the palladium compound.
The carbon monoxide, ethylene and propylene are liquid phase polymerized in a mixed solvent of acetic acid and water to produce a linear terpolymer. As the mixed solvent, a mixture of 100 parts by weight of acetic acid and 2 to 30 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 deteriorate the heat stability in the process. If the amount is more than 30 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 extruded by an extruder to finally obtain a blend composition. The blend is produced by putting into a twin-screw extruder, melt-kneading and extruding.
In this case, the extrusion temperature is preferably 230 to 260 ° C, and the screw rotation speed is preferably in the range of 100 to 300 rpm. If the extrusion temperature is less than 230 캜, kneading may not occur properly, and if the extrusion temperature exceeds 260 캜, problems related to the heat resistance of the resin may occur.
A polyketone refrigerator door closure can be manufactured by preparing a resin by the above-mentioned method and injecting it.
The polyketone refrigerator door closure manufactured according to the present invention has been found to have excellent abrasion resistance.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not construed as being limited by these embodiments.
Example One
The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 78 deg. C and the second stage at 84 deg. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 85 to 15. The melting point of the polyketone terpolymer was 220 占 폚, the LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, and the MWD was 2.0. The polyketone terpolymer prepared above was molded into a pellet on an extruder using a twin screw having a diameter of 40 mm and operated at 250 rpm and L / D = 32, and then injection molded to prepare a refrigerator door closure specimen .
Example 2
The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 78 deg. C and the second stage at 84 deg. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 85 to 15. The melting point of the polyketone terpolymer was 220 占 폚, the LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, and the MWD was 2.0. The polyketone terpolymer and the polytetrafluoroethylene resin thus prepared were fed to prepare a composition. The composition thus prepared was extruded through a pelletizer on an extruder using a twin screw having a diameter of 40 mm and an L / D of 32, which was operated at 250 rpm. (pellet), and then injection molded into a refrigerator door closure specimen.
Example 3
The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 78 deg. C and the second stage at 84 deg. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 85 to 15. The melting point of the polyketone terpolymer was 220 占 폚, the LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, and the MWD was 2.0. The polyketone terpolymer and the thermoplastic polyurethane resin prepared above were fed to prepare a composition. The composition thus prepared was pelletized on an extruder using a twin screw having a diameter of 40 mm and an L / D of 32, which was operated at 250 rpm. ), And then injection molded into a refrigerator door closure specimen.
Comparative Example One
A refrigerator door closure specimen was prepared in the same manner as in Example 1 except that the polyoxymethylene resin used as the material of the refrigerator door closure was used.
Property evaluation
The prepared pellets of the above examples were injection-molded to prepare refrigerator door closure samples. The properties of the samples were evaluated in the following manner in comparison with the specimens of the comparative examples. The results are shown in Table 1 below.
1. Friction Coefficient: The kinematic friction coefficient is a value that can represent the degree of kinetic friction. The larger the kinetic friction coefficient, the greater the frictional force, and the smaller the value, the smaller the frictional force.
2. Evaluation of abrasion: The test was carried out in accordance with JIS K7218 (test condition: 50 rmp, 3 km wear at 150 N).
3. Noise evaluation: After the noise was measured, it was indicated by o when it was 40dB or more and when it was less than 40dB, it was marked by x.
(g)
As can be seen from Table 1, the friction coefficient and abrasion resistance of Comparative Example 1 were smaller than those of Comparative Example 1, so that the friction force was smaller and the abrasion resistance was improved. Accordingly, the refrigerator door closure manufactured through the embodiment of the present invention exhibits better wear resistance than the comparative example used as a conventional refrigerator door closure material, and is less suitable for application as a refrigerator door closure.
Claims (5)
The ligand of the catalyst composition used in the polymerization of the polyketone is selected from the group consisting of bis (2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) ),
Wherein the polyketone refrigerator door closure has a friction coefficient of 0.13 to 0.14 and a worn amount of 0.001 to 0.006 g in accordance with JIS K7218.
- [- CH2CH2-CO] x- (1)
- [- CH2 --CH (CH3) - CO] y - (2)
(x and y represent mol% of each of the general formulas (1) and (2) in the polymer).
Wherein the polyketone polymer further comprises a polytetrafluoroethylene resin or a thermoplastic polyurethane resin.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150074034A KR101807612B1 (en) | 2015-05-27 | 2015-05-27 | Polyketone refrigerator door closure |
| EP15857807.0A EP3219744A4 (en) | 2014-11-07 | 2015-10-19 | Polyketone resin composition with excellent wear resistance |
| JP2017523870A JP6576447B2 (en) | 2014-11-07 | 2015-10-19 | Polyketone resin composition with excellent wear resistance |
| PCT/KR2015/011026 WO2016072641A1 (en) | 2014-11-07 | 2015-10-19 | Polyketone resin composition with excellent wear resistance |
| CN201580060244.1A CN107075244A (en) | 2014-11-07 | 2015-10-19 | Polyketone resin composition with superior abrasion resistance |
| US15/524,422 US20180162996A1 (en) | 2014-11-07 | 2015-10-19 | Polyketone resin composition with excellent wear resistance |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150074034A KR101807612B1 (en) | 2015-05-27 | 2015-05-27 | Polyketone refrigerator door closure |
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| Publication Number | Publication Date |
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| KR20160139371A KR20160139371A (en) | 2016-12-07 |
| KR101807612B1 true KR101807612B1 (en) | 2017-12-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1020150074034A KR101807612B1 (en) | 2014-11-07 | 2015-05-27 | Polyketone refrigerator door closure |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007131651A (en) | 2005-11-08 | 2007-05-31 | Asahi Kasei Chemicals Corp | Impact resistant polyketone resin composition and molded article thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007131651A (en) | 2005-11-08 | 2007-05-31 | Asahi Kasei Chemicals Corp | Impact resistant polyketone resin composition and molded article thereof |
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