KR101888071B1 - Polyketone resin composition having improved processing stability and mechanical properties - Google Patents

Abstract

Provided is a polyketone resin composition with improved processing stability and mechanical properties. To this end, the polyketone resin composition comprises: linearly alternated polyketone composed of at least one olefin-based unsaturated hydrocarbon and carbon monoxide; and a monomer having a carbonate structure which is one or more selected from the group consisting of ethylene carbonate, dimethyl carbonate, propylene carbonate, and diphenyl carbonate.

Description

[0001] The present invention relates to a polyketone resin composition having improved processing stability and mechanical properties,

TECHNICAL FIELD The present invention relates to a polyketone resin composition having improved processing stability and mechanical properties, and more particularly, to a polyketone resin composition containing a polyketone resin, ethylene carbonate, dimethyl carbonate, propylene carbonate and diphenyl carbonate and diphenyl carbonate. The present invention also relates to a polyketone composition which is improved in mechanical properties and improved in mechanical properties by using a composition comprising a monomer having a carbonate structure.

Polyketone (PK) is a low-cost material for general engineering plastic materials such as polyamide, polyester, and polycarbonate, and has excellent properties such as heat resistance, chemical resistance, fuel permeability and abrasion resistance. .

The polyketone having the above characteristics can be produced by reacting carbon monoxide (CO) and an olefin such as ethylene or propylene as a catalyst with a transition metal complex such as palladium (Pd) or nickel (Ni) It is already known that carbon monoxide and olefin are obtained by alternately bonding with each other by using a polymerization initiator (Industrial Materials, December, 5, 1997). On the other hand, 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 method for producing a polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of a nonhydrohalogenic acid having a pKa of less than 6, and a catalyst that is a bidentate ligand of phosphorus .

On the other hand, most of the conventional techniques for improving the processing stability of polyketone use additives. In this case, however, the processing stability is improved, but the physical properties such as impact strength are very low. Accordingly, there is a need for a polyketone composition having improved mechanical properties as processing stability is improved.

) U.S. Published Patent Application No. 2016-0002393 Korean Registered Patent No. 1,539,680 European Patent No. 01117724 ) United States Patent No. 09428645

In order to solve the above-mentioned problems, the present invention provides a polyketone comprising one or more selected from the group consisting of ethylene carbonate, dimethyl carbonate, propylene carbonate and diphenyl carbonate, It is an object of the present invention to provide a polyketone composition improved in processing stability and mechanical properties by adding a monomer having a carbonate structure of two or more.

In order to accomplish the above object, the present invention provides a process for producing a polyolefin resin composition comprising a linear alternating polyketone resin composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon, ethylene carbonate, dimethyl carbonate, propylene carbonate, Diphenyl carbonate, and the composition ratio of the monomer having the carbonate structure to the total weight of the polyketone composition is 1 to 10% by weight And a polyketone composition having improved processing stability and mechanical properties.

And the monomer having the carbonate structure is one or two selected from the group consisting of ethylene carbonate and propylene carbonate.

Specifically, the long-term stay evaluation of the polyketone composition at 220 DEG C and 100 rpm showed that the max torque was 60 Nm or less and the max cylinder temperature was 260 DEG C or less. (Bis (2-methoxyphenyl) phosphine) and (cyclohexane (bis (methylene)) bis Bis (methylene)) bis (bis (2-methoxyphenyl) phosphine).

The composition of the present invention improves the processing stability and improves the mechanical properties, which makes it possible to expand the market to extrusion, film market, and injection product containing flame retardant, which was difficult to apply due to limitations of physical properties and processing stability of polyketone .

FIG. 1 is a graph showing Torque of a Haake Mixer staying evaluation result in Examples 2 and 5 and Comparative Example 1 in order to confirm the effect of improving the processing stability of the present invention.
FIG. 2 is a graph showing the temperature difference of the cylinders of the result of the Haake Mixer staying evaluation in Examples 2 and 5 and Comparative Example 1 to confirm the effect of improving the processing stability of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention relates to a process for producing a polyketone which comprises reacting a polyketone with a monomer having a carbonate structure which is one or more selected from the group consisting of ethylene carbonate, dimethyl carbonate, propylene carbonate and diphenyl carbonate To provide a polyketone composition having improved processing stability and mechanical properties.

First, the polyketone resin used in the present invention is an engineering plastic and recently developed as a new resin, it is excellent in mechanical properties such as impact strength and molding characteristics, and is excellent in thermoplastic properties It is synthetic resin. 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.

Polyketone resin has lower moisture absorption than polyamide material, so 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.

Hereinafter, the process for producing the polyketone will be described.

The production process 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, A process for producing a polyketone by terephthalic copolymerization of an ethylenic and a propylenically unsaturated compound is characterized in that a mixed solvent of 70 to 90% by volume of acetic acid and 10 to 30% by volume of water is used as a liquid medium and benzophenone .

Here, the liquid medium is characterized in that a mixed solvent of acetic acid and water is used without using methanol, dichloromethane, or nitromethane, which has conventionally been used for producing polyketones. This is because the use of a mixed solvent of acetic acid and water as a liquid medium for the production of polyketone can improve the catalytic activity while reducing the manufacturing cost of the polyketone.

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. Therefore, it is preferable to use a mixed solvent comprising 70 to 90% by volume of acetic acid and 10 to 30% by volume of water as a liquid medium.

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).

       [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.

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 then performing a step of acquiring

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, tricyclodecene, 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, most preferably ethylene, and 120 mol% propylene is added in the production of the terpolymerized polyketone.

       Here, it is preferable to adjust the charging ratio of the carbon monoxide and the ethylenic unsaturated compound to 1: 1 to 2 (molar ratio) and to adjust the propylene to 1 to 20 mol% based on the total mixed gas. In the production of polyketones, it is general to set the mixing ratio of carbon monoxide and ethylenic unsaturated compound to 1: 1. However, in the present invention in which a mixed solvent of acetic acid and water is used as a liquid medium and benzophenone is added during polymerization, It has been found that when the feed ratio of the unsaturated compound is adjusted to 1: 1 to 2 and the propylene is adjusted to 1 to 20 mol% based on the total mixed gas, not only the processability but also the catalyst activity and the intrinsic viscosity can be simultaneously achieved. When the amount of propylene is less than 1 mol%, the effect of the ternary copolymerization to lower the melting temperature can not be obtained. When the amount exceeds 20 mol%, the intrinsic viscosity and the improvement of the catalytic activity are inhibited, so that the addition ratio is adjusted to 1 to 20 mol% .

      In addition, in the process, a mixed solvent of acetic acid and water is used as a liquid medium, benzophenone is added during polymerization, and carbon monoxide, an ethylenically unsaturated compound and one or more olefinic unsaturated compounds are added to improve the catalytic activity and intrinsic viscosity of the polyketone In addition, in the prior art, it is possible to produce a terpolymer having a high intrinsic viscosity at a polymerization time of only about 12 hours, unlike the case where the polymerization time has to be set to at least 10 hours in order to improve the intrinsic viscosity.

      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.

      As the polymerization method, 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 are used. 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 is generally 40 to 180 占 폚, preferably 50 to 120 占 폚. 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.

As described above, the polyketone is produced through a polymerization process according to the above-described production process.

On the other hand, the polyketone polymer of the present invention is a linear alternating structure and substantially contains carbon monoxide for each unsaturated hydrocarbon molecule. Ethylenically unsaturated hydrocarbons suitable for use as precursors of polyketone polymers include ethynes with up to 20 carbon atoms, preferably up to 10 carbon atoms, alpha -olefins (e.g., propene, 1-butene, ), Aliphatic hydrocarbons such as isobutene, 1-hexene and 1-octene, or aryl aliphatic hydrocarbons having an aryl substituent on the aliphatic molecule, in particular ethylenically unsaturated carbon atoms Lt; / RTI > is an aryl aliphatic hydrocarbon in which an aryl substituent is formed. Examples of the aryl aliphatic hydrocarbon in the ethylenic unsaturated hydrocarbon include styrene, p-methylstyrene, p-ethylstyrene, and m-isopropyl styrene. The polymer preferably used in the present invention is a linear terpolymer of an olefin, such as carbon monoxide, ethene, and a second ethylenically unsaturated hydrocarbon having at least three carbon atoms (especially propene).

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)] y-

In the general formula (2), G is an ethylenically unsaturated hydrocarbon, particularly a portion obtained from an ethylenically unsaturated hydrocarbon having at least three carbon atoms, and x: y is preferably at least 1: 0.01.

In another embodiment, the polyketone polymer is a copolymer comprising repeating units represented by the 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 in that the meltability and processability are inferior. When the value of y / x is more than 0.3, the mechanical properties are poor. Further, y / x is more preferably 0.03 to 0.1.

       - [- 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 1.5 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 to 300 占 폚, and is generally 210 to 270 占 폚. 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, And more preferably 1.0 dl / g to 2.0 dl / g. If the intrinsic viscosity is less than 1.0 dl / g, the mechanical properties are deteriorated. If the intrinsic viscosity exceeds 2.0 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.

Specifically, the polyketone composition improved in processing stability and mechanical properties of the present invention comprises a linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon, and a group consisting of ethylene carbonate, dimethyl carbonate, propylene carbonate and diphenyl carbonate And a monomer having a carbonate structure selected from the group consisting of a monomer having a carbonate structure and a monomer having a carbonate structure.

       The content of the carbonate monomer of the present invention is preferably 1 to 10% by weight, more preferably 1 to 5% by weight based on the total composition. If the content of the carbonate monomer is less than 1% by weight, the effect of improving the impact strength and the melt index may be very low. If the content is more than 10% by weight, the tensile strength may be too low. Meanwhile, the polyketone composition of the present invention preferably has a max torque of 60 Nm or less and a max cylinder temperature of 260 캜 or less as a result of evaluation of a Haake Mixer long-term stay at 220 캜 and 100 rpm. This is because the processing stability is better than the torque and temperature in this range.

Hereinafter, the production method for producing the polyketone composition is as follows.

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 blending the polyketone resin with polybutylene terephthalate (PBT) or nylon 6 (PA6) and reinforcing fibers to form a composition, but the present invention is not limited thereto.

As the palladium compound constituting the catalyst composition, palladium acetate can be used. The amount of the palladium compound to be used is preferably 10 -3 to 10 -1 mole, but is not limited thereto.

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, ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Methylene)) bis (bis (2-methoxyphenyl) phosphine) and (cyclohexane-1,1-diylbis (methylene)) bis Or more, 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 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 monomer having a carbonate structure and then extruded with an extruder to finally obtain a polyketone composition. The blend may be prepared by charging it into a twin-screw extruder and melt-kneading and extruding it.

       At this time, the extrusion temperature is preferably 200 to 260 DEG C and the screw rotation speed is preferably 100 to 300 rpm. When the extrusion temperature is less than 200 ° C, kneading may not occur properly, and when the extrusion temperature is higher than 260 ° C, a problem relating to heat resistance of the resin may occur. If the screw rotation speed is less than 100 rpm, smooth kneading may not occur.

       Hereinafter, the present invention will be described in detail 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.

       [Example 1]

       Linear alternating polyketones comprised of carbon monoxide and ethylene and propene were prepared from palladium acetate, trifluoroacetic acid, and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) The content of trifluoroacetic acid with respect to palladium is 10 times the molar ratio and is subjected to two steps of 1 stage of polymerization temperature of 78 DEG C and 84 DEG C. The carbon monoxide in the polyketone prepared above is 50 mol The melting point of the polyketone was 220 占 폚, the molecular weight measured by GPC (Gel Permeation Chromatography) was Mn = 52,500, Mw = 141,400, the molecular weight dispersion degree PDI = 2.69. The thus prepared terpolymer is named M330A.

       97% by weight of the polyketone terpolymer (M330A) and 3% by weight of ethylene carbonate were added to prepare a composition. The composition thus prepared was subjected to a twin screw operation with a diameter of 40 cm and an L / D of 32 Lt; RTI ID = 0.0 > pellets < / RTI > on an extruder.

       [Example 2]

       The same as Example 1 except that 95 weight% of polyketone terpolymer M330A and 5 weight% of ethylene carbonate.

       [Example 3]

       Except that 90 wt% of polyketone terpolymer M330A and 10 wt% of ethylene carbonate were used.

[Example 4]

A polyketone terpolymer M630A having an increased molecular weight was prepared in the same manner as in Example 1. The molecular weight measured by GPC (Gel Permeation Chromatography) was Mn = 79,000, Mw = 220,600, and molecular weight dispersion degree PDI = 2.77. The same procedure as in Example 1 was performed except that 95% by weight of the terpolymer M630A thus prepared and 5% by weight of ethylene carbonate were used.

[Example 5]

Except that 95 wt% of polyketone terpolymer M330A and 5 wt% of propylene carbonate were used.

[Comparative Example 1]

A specimen was prepared in the same manner as in Example 1 except that 100 weight% of polyketone M330A was used.

[Comparative Example 2]

A specimen was prepared in the same manner as in Example 1 except that 100 wt% of polyketone M630A having a high MW was used.

[Property evaluation]

Molecular weight distribution of the terpolymers M330A and M630A in Examples 1 and 4 as measured by GPC is shown in Table 1.

The physical properties of the specimens prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were evaluated, and the results are shown in Tables 2 and 3 below.

1. Melt Index: Measured according to ASTM D1238 at a temperature of 240 DEG C under a load of 2.16 kg and expressed as the weight (g) of the polymer that has been melted for 10 minutes.

2. Tensile strength: ASTM D638.

3. Impact strength: [24] C according to ASTM D256.

4. Results of Haake Mixer Long-term Stay Evaluation: While the outer jacket temperature of the Haake mixer was kept constant at 220 ° C, 180 g of the sample was put into the chamber, the two rotors were rotated at a speed of 100 rpm, .

division Mn
(g / mol) Mw
(g / mol) Mz
(g / mol) PDI M330A 52,500 141,400 318,800 2.69 M630A 79,000 220,600 569,100 2.77

division Content (weight ratio)
(PK / EC / PC) The tensile strength
(MPa) Elongation
(%) Flexural strength
(MPa) Bending modulus
(MPa) Impact strength
(kJ / m ² ) MI
(g / 10 min) M330A M630A EC PC Yield 0hr Example 1 97 - 3 - 57 263 51 1198 12.0 73 Example 2 95  - 5 - 53 305 46 1028 14.1 78 Example 3 90  - 10 - 54 287 46 1055 19.6 90 Example 4  - 95 5 - 51 291 43 941 23.6 9 Example 5 95 - - 5 51 285 42 907 12.3 86 Comparative Example 1 100  -  - - 61 244 63 1570 9 58 Comparative Example 2  - 100 -  - 65  278 53 1380 12.3 8

PK: polyketone {M330A, M630A: Hyosung Corporation}, EC: ethylene carbonate, PC: propylene carbonate

As shown in Table 2, the impact strength and the melt index (fluidity) of Examples were increased and the mechanical properties were improved.

division Resin composition Haake
Max torque
Nm) Haake
Max running time
(min) Haake
Temp difference (° C)
(max - initial value 220 ° C) Comparative Example 1 PK (M330A) > 60
@ 160 minutes 175 37
@ 160 minutes Example 2 PK-EC (95: 5) ~ 18
@ 300 minutes > 300 17
@ 300 minutes Example 5 PK-PC (95: 5) ~ 25
@ 300 minutes > 300 30
@ 300 minutes

PK: polyketone (M330A Hyosung), EC: ethylene carbonate, PC: propylene carbonate

       In Comparative Example 1, the maximum cylinder temperature was 257 ° C. In Examples 2 and 5, the maximum cylinder temperatures were 237 ° C and 250 ° C, respectively.

       As shown in Table 3, the maximum torque value is small, Max running time is long, and the temperature change is small even when the residence time is increased, as compared with the comparative example.

       Therefore, the polyketone composition prepared through the examples was improved in terms of the mechanical properties as well as the processing stability, and thus it was evaluated to be suitable for use as tubes, pipes, films for food packaging, and general injection parts.

Claims (4)

A linear alternating polyketone comprised of carbon monoxide and at least one olefinically unsaturated hydrocarbon; And
A monomer having a carbonate structure which is one or two selected from the group consisting of ethylene carbonate and propylene carbonate,
The composition ratio of the monomers having the carbonate structure is 1 to 5% by weight based on 100% by weight of the total polyketone composition,
The ligand of the catalyst composition used in the polyketone polymerization is (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine)
The maximum torque is 60 Nm or less and the maximum cylinder temperature is 260 占 폚 or less as a result of evaluation of the long-term stay of Haake Mixer at 220 占 폚 and 100 rpm. delete delete delete

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