WO2018212488A1 - Polyketone alloy resin composition - Google Patents

Abstract

The present invention provides a polyketone alloy composition with improved process stability and mechanical properties, the composition being characterized in that one or two polyalkylene carbonates selected from the group consisting of polypropylene carbonate (PPC) and polyethylene carbonate (PEC) are added to a linear alternative polyketone composed of carbon monoxide and at least one olefin-based unsaturated hydrocarbon.

Description

Polyketone Alloy Resin Composition

The present invention relates to a polyketone alloy resin composition having improved processing stability and mechanical properties, and more particularly, to improving processing stability, comprising adding polyalkylene carbonate, an amorphous polymer, to polyketone. At the same time the mechanical properties also relate to improved polyketone alloy compositions.

Polyketone (PK) is a material that has lower raw materials and polymerization process costs than general engineering plastic materials such as polyamide, polyester, and polycarbonate. Polyketone (PK) has excellent properties such as heat resistance, chemical resistance, fuel permeability, and abrasion resistance. It is widely applied to.

Polyketone having the above characteristics is a catalyst based on carbon monoxide (CO) and olefins such as ethylene and propylene to form transition metal complexes such as palladium (Pd) and nickel (Ni). It is already known that carbon monoxide and olefins are obtained by alternating bonding with one another by polymerization by means of polymerization (Industrial Materials, December issue, page 5, 1997). On the other hand, there is a growing interest in a group of linear alternating polymers consisting 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 and ethylene and other olefinically unsaturated hydrocarbons such as propylene.

The process for producing polyketone polymers is usually a compound of a Group VIII metal selected from palladium, cobalt or nickel, anions of non-hydrohalogenic acid, phosphorus and arsenic Or a catalyst composition produced from a bidentate ligand of Antimon.

US Pat. No. 4,843,144 describes a process for preparing polymers 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. Is starting.

On the other hand, the prior art for improving the processing stability of the polyketone, there is a method using an additive such as a plasticizer or a lubricant, but this has the effect of complementing the workability in the short term, but there is a limit in improving the long-term processing stability. In addition, in the case of using the additive, the processing stability is improved, but the physical properties such as impact strength is very low. Accordingly, there is a need for a polyketone composition having improved long-term processing stability and a polyketone composition having improved mechanical properties while improving processing stability.

In order to solve the above problems, an object of the present invention is to add a polyalkylene carbonate (polyalkylene carbonate) to the polyketone to provide a polyketone alloy composition with improved processing stability and mechanical properties.

In order to achieve the above technical problem, the present invention uses an alloy made by adding polyalkylene carbonate to the linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon, in the extrusion and injection process The present invention provides a polyketone alloy composition having improved long-term processing stability by delaying crosslinking and degradation that may occur during long-term operation.

At this time, the composition ratio of the polyalkylene carbonate to the total weight of the polyketone alloy composition is a composition ratio of 5 to 90% by weight, the polyalkylene carbonate is polypropylene carbonate (PPC; Polypropylene carbonate) and polyethylene carbonate (PEC; Polyethylene carbonate) and one or two selected from the group consisting of.

Here, the maximum running time of the polyketone alloy composition at 220 ° C. and 100 rpm may be 300 minutes or more as a result of a long-term stay evaluation of the Hake Mixer.

In addition, the number average molecular weight of the polypropylene carbonate is preferably 2,000 to 100,000, and the number average molecular weight of the polyethylene carbonate is preferably 100,000 to 300,000.

In this case, when the polyethylene carbonate is used as the polyalkylene carbonate, the composition ratio of polyethylene carbonate is 1 to 20% by weight based on the total weight of the polyketone alloy composition, and the number average molecular weight of the polyethylene carbonate may be 10,000 to 300,000. Herein, the polyketone alloy composition may have a maximum running time of 140 minutes or more as a result of the Hake Mixer long-term residence evaluation at 220 ° C. and 100 rpm.

In addition, the ligand of the catalyst composition used in the polyketone polymerization is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) Phosphine) and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine).

The polyketone alloy composition of the present invention reduces the gel, carbonization, black spots, etc. generated during long-term retention due to the stagnation of the resin in the process of extrusion, injection, etc. to prevent product defects or damage to processing equipment. It can increase the production efficiency, and improve the mechanical properties such as impact strength and flexural modulus, thereby expanding the product range.

1 is a graph showing the cross over time (COT) in Examples 1, 2 and Comparative Example 1 to confirm the effect of improving the processing stability of the present invention.

Figure 2 is a graph showing the Torque Haake Mixer retention evaluation results in Examples 1 and 2 and Comparative Example 1 to confirm the effect of improving the processing stability of the present invention.

3 is a graph showing the difference in temperature of the cylinders of Haake Mixer retention evaluation in Examples 1 and 2 and Comparative Example 1 to confirm the effect of improving the processing stability of the present invention.

4 is a graph showing Melt viscosity (MV) of Examples 1 and 2 and Comparative Example 1 of the present invention.

5 is a graph showing the thermogravimetric analysis (TGA) of Examples 1 and 2, Comparative Example 1 and polyethylene carbonate (PEC) of the present invention.

6 is a graph showing the molecular weight of Examples 1 and 2, Comparative Example 1 and polyethylene carbonate of the present invention.

7 is a scanning electron microscope (SEM) photograph of the fracture surface of the impact specimen of Example 2 of the present invention.

8 is a photograph of the colors of Examples 1 and 2 and Comparative Example 1 of the present invention.

Figure 9 is a graph showing the Torque Mixer (Haake Mixer) retention evaluation results in Examples 3, 11 to 13 and Comparative Example 2 to confirm the effect of improving the processing stability of the present invention.

10 is a graph showing the temperature difference of the cylinders of Hake Mixer retention evaluation in Examples 3, 11 to 13 and Comparative Example 2 in order to confirm the effect of improving the processing stability of the present invention.

Hereinafter, the present invention will be described in detail with reference to the drawings.

The present invention also provides a polyketone alloy composition having improved long-term processing stability and mechanical properties by adding polyalkylene carbonate to the polyketone.

First, the polyketone resin used in the present invention is an engineering plastic and is a recently developed new resin, and is a thermoplastic synthetic resin that is usefully applied as a material for various molded products or parts due to its excellent mechanical properties and molding properties such as impact strength. to be. Mechanical properties of the polyketone resin belongs to the category of high performance plastics, and is a polymer material that synthesizes carbon monoxide as a raw material.

Polyketone resin has low moisture absorption compared to polyamide material, so it is possible to design various products with little change in dimensions and physical properties due to moisture absorption. In particular, polyketone resin has a lower density than aluminum, making it suitable for weight reduction.

Hereinafter, the manufacturing process of the said polyketone is demonstrated.

The process for preparing polyketones is characterized by the presence of carbon monoxide in a liquid medium in the presence of an organometallic complex catalyst comprising a ligand having an element of group (a) Group 9, Group 10 or Group 11, and group (b) Group 15. In the method for producing polyketone by terpolymerization of ethylenic and propylene unsaturated compounds, a mixed solvent consisting of 70 to 90% by volume of acetic acid and 10 to 30% by volume of water is used as a liquid medium. It is characterized by the addition.

In this case, a mixed solvent consisting of acetic acid and water is used as a liquid medium, without using methanol, dichloromethane, or nitromethane, which have been mainly used in the production of polyketone. This is because by using a mixed solvent of acetic acid and water as the liquid medium in the production of the polyketone it is possible to improve the catalytic activity while reducing the production cost of the polyketone.

When a mixed solvent of acetic acid and water is used as the liquid medium, when the concentration of water is less than 10% by volume, the catalytic activity is less affected. However, when the concentration is more than 10% by volume, the catalytic activity rapidly increases. On the other hand, when the concentration of water exceeds 30% by volume, catalytic activity tends to decrease. Therefore, it is preferable to use a mixed solvent composed of 70 to 90 vol% acetic acid and 10 to 30 vol% water as the liquid medium.

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

Examples of the Group 9 transition metal compound in the Group 9, 10 or 11 transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamate salts, sulfonates, and the like. Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, trifluoro ruthenium acetate, ruthenium acetylacetate, and trifluoromethane sulfonate ruthenium.

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

Examples of the Group 11 transition metal compound include copper or silver complexes, carbonates, phosphates, carbamates, sulfonates, and the like, and specific examples thereof include copper acetate, trifluoroacetate, copper acetylacetate, silver acetate, tri Silver fluoroacetic acid, silver acetyl acetate, silver trifluoromethane sulfonic acid, etc. are mentioned.

Among these, inexpensive and economically preferable transition metal compounds (a) are nickel and copper compounds, and preferred transition metal compounds (a) are palladium compounds in terms of yield and molecular weight of polyketones, and in terms of improving catalytic activity and intrinsic viscosity. Most preferably, palladium acetate is used in the process.

Examples of the ligand (b) having a group 15 atom include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picolin , Nitrogen ligands such as 2,2'-bikinolin, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) Butane, 1,3-bis [di (2-methyl) phosphino] propane, 1,3-bis [di (2-isopropyl) phosphino] propane, 1,3-bis [di (2-methoxyphenyl ) Pinospino] propane, 1,3-bis [di (2-methoxy-4-sulfonic acid-phenyl) phosphino] propane, 1,2-bis (diphenylphosphino) cyclohexane, 1,2-bis (Diphenylphosphino) benzene, 1,2-bis [(diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, 1,2- Bis [[di (2-methoxy-4-sulfonate-phenyl) phosphino] methyl] benzene, 1,1'-bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) Spinosyns; there may be mentioned a ligand, such as propane.

Among them, the ligand (b) having an element of Group 15 is a phosphorus ligand having an atom of Group 15, and particularly, in view of the yield of polyketone, a phosphorus ligand is preferably 1,3-bis [di (2- Methoxyphenyl) phosphino] propane, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, and 2-hydroxy-1,3-bis [in terms of molecular weight of the polyketone. Di (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) phosphino] propane, and do not require an organic solvent in terms of safety Water-soluble 1,3-bis [di (2-methoxy-4-sulfonate-phenyl) phosphino] propane, 1,2-bis [[di (2-methoxy-4-sulfonate-phenyl) phosphino ] Methyl] benzene, the synthesis | combination is easy, it is available in large quantities, and economically preferable is 1, 3-bis (diphenyl phosphino) propane and 1, 4-bis (diphenyl phosphino) butane. Preferred ligand (b) having an atom of group 15 is 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis (diphenylphosphino) propane, most preferably 1,3-bis [di (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2 Methoxyphenyl) phosphine).

[Formula 1]

((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) of Formula 1 is a polyketone introduced to date Activity equivalent to 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, known to exhibit the highest activity in the polymerization catalyst The structure is simpler and has a lower molecular weight. As a result, the present invention is able to provide a novel polyketone polymerization catalyst, while maintaining the highest activity as a polyketone polymerization catalyst in the art while further reducing the production cost and cost. The method for preparing a ligand for a polyketone polymerization catalyst is as follows. Using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and sodium hydride (NaH) ((2,2-dimethyl Provided is a method for producing a ligand for a polyketone polymerization catalyst, characterized by obtaining -1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine). . The method for preparing a ligand for a polyketone polymerization catalyst of the present invention is conventionally 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane Unlike the synthesis method of ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially mass synthesized.

It is also preferable to use (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine) as the ligand used in the polymerization catalyst. The method for synthesizing the ligand is as follows.

In a preferred embodiment, the method for preparing a ligand for a polyketone polymerization catalyst of the present invention is (a) adding bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) to a reaction vessel under a nitrogen atmosphere and hydrogenated at room temperature. Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the obtained mixture, followed by stirring to react; (c) adding and stirring methanol after completion of the reaction; (d) adding toluene and water, washing the oil layer with water after separating the layers, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue is recrystallized under methanol ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) It can be carried out by obtaining a step.

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) to be used varies uniformly since the appropriate value varies depending on the type of the ethylenic and propylene unsaturated compounds selected or other polymerization conditions. Although not limited, it is usually 0.01-100 mmol, preferably 0.01-10 mmol, per liter of the capacity of the reaction zone. The capacity of the reaction zone means the capacity of the liquid phase of the reactor. The amount of the ligand (b) to be used is not particularly limited, but is usually 0.1 to 3 mol, preferably 1 to 3 mol, per mol of the transition metal compound (a).

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

Examples of ethylenically unsaturated compounds copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 Α-olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and α-methylstyrene; Cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetra Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Acrylic esters, such as ethyl acrylate and methyl acrylate, etc. are mentioned. Among these, preferred ethylenically unsaturated compounds are α-olefins, more preferably α-olefins having 2 to 4 carbon atoms, most preferably ethylene, and 120 mol% propylene is added in the production of terpolymer copolyketones.

Here, it is preferable to adjust the input ratio of carbon monoxide and ethylenically unsaturated compound to 1 to 2 (molar ratio) and to adjust the propylene to 1 to 20 mol% relative to the total mixed gas. In the production of polyketone, it is common to set the ratio of carbon monoxide and ethylenically unsaturated compound to 1: 1, but in the present invention using a mixed solvent of acetic acid and water as a liquid medium and adding benzophenone during polymerization, carbon monoxide and ethylenic When the input ratio of the unsaturated compound is 1: 1 to 2 and the propylene is adjusted to 1 to 20 mol% relative to the total mixed gas, it was found that not only the workability is improved but also the catalytic activity and the intrinsic viscosity can be simultaneously achieved. If the input amount of propylene is less than 1 mol%, the effect of terpolymer copolymerization to lower the melting temperature cannot be obtained. If it exceeds 20 mol%, there is a problem of inhibiting the intrinsic viscosity and the improvement of catalyst activity. Therefore, the input ratio is controlled to 1 to 20 mol%. It is desirable to.

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 and ethylenically unsaturated compound and one or more olefinically unsaturated compounds are added to the catalytic activity and intrinsic viscosity of the polyketone. In addition to the improvement, in the prior art, the polymerization time should be at least 10 hours to improve the intrinsic viscosity, but it is possible to prepare a terpolymer copolymer polyketone having a high intrinsic viscosity even if the polymerization time is about 12 hours.

Ternary copolymerization of carbon monoxide, the ethylenically unsaturated compound and the propylene unsaturated compound is an organometallic complex comprising a Group 9, Group 10 or Group 11 transition metal compound (a) and a ligand (b) having an element of Group 15 As a result of the catalyst, the catalyst is produced by contacting the two components. Arbitrary methods can be employ | adopted as a method of making it contact. That is, you may make and use the solution which mixed two components previously in a suitable solvent, and may respectively supply two components separately to a polymerization system, and may contact them in a polymerization system.

As the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, a gas phase polymerization method in which a small amount of a polymer is impregnated with a high concentration of a catalyst solution are used. The polymerization may be either batchwise or continuous. The reactor used for superposition | polymerization can use a well-known thing as it is or processing it. There is no restriction | limiting in particular about polymerization temperature, Generally 40-180 degreeC, Preferably 50-120 degreeC is employ | adopted. Although there is no restriction | limiting also about the pressure at the time of superposition | polymerization, Usually, it is normal pressure-20 MPa, Preferably it is 4-15 MPa.

In the above, polyketone is manufactured through a polymerization process according to the manufacturing process as described above.

On the other hand, the polyketone polymer of the present invention is a linear alternating structure, and substantially contains carbon monoxide for each molecule of unsaturated hydrocarbon. Ethylenically unsaturated hydrocarbons suitable for use as precursors of polyketone polymers are ethene, α-olefins (e.g. propene, 1-butene) having up to 20 carbon atoms, preferably up to 10 carbon atoms. ), Aliphatic hydrocarbons such as isobutene, 1-hexene and 1-octene), or arylaliphatic hydrocarbons having aryl substituents on aliphatic molecules, in particular ethylenically unsaturated carbon atoms Arylaliphatic hydrocarbon with an aryl substituent on the phase. Examples of the arylaliphatic hydrocarbons among the ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene, m-isopropyl styrene, and the like. Polymers preferably used in the present invention are linear terpolymers of carbon monoxide with ethene and α-olefins such as second ethylenically unsaturated hydrocarbons having at least three carbon atoms (especially propene).

When using the polyketone terpolymer as the main polymer component of the blend of the present invention, for each unit containing the second hydrocarbon moiety in the terpolymer, there are at least two units containing the ethylene moiety. It is preferable that there are 10-100 units containing a 2nd hydrocarbon part.

In one embodiment, the polyketone polymer may include a unit represented by the following formula (2) as a repeating unit.

[Formula 2]

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

In the formula (2), G is an ethylenically unsaturated hydrocarbon, in particular, a part obtained from 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 composed of repeating units represented by General Formulas (1) and (2), and it is preferable that y / x is 0.03 to 0.3. When the value of the y / x value is less than 0.03, there is a limit inferior in meltability and workability, and when it exceeds 0.3, mechanical properties are inferior. Further, y / x is more preferably 0.03 to 0.1.

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

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

On the other hand, the preferred intrinsic viscosity (LVN) of the polyketone resin is 0.5 to 10 dl / g, more preferably 0.8 to 4 dl / g, 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 lowered. If it exceeds 10 dl / g, the workability may be reduced.

Particularly preferred are polyketone polymers having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer depend on the molecular weight, on whether the polymer is a copolymer or terpolymer, and in the case of terpolymers, on the nature of the second hydrocarbon moiety present. Melting | fusing point of the conversion of the polymer used by this invention is 175-300 degreeC, and is 210-270 degreeC generally. The ultimate viscosity number (LVN) of the polymer measured at 60 ° C. using a standard tubular viscosity measuring device and HFIP (Hexafluoroisopropylalcohol) is 0.5 dl / g to 10 dl / g, more preferably 0.8 dl / g to 4 dl / g, More preferably, they are 1.0 dl / g-2.0 dl / g. At this time, if the limiting viscosity number is less than 1.0 dl / g mechanical properties are inferior, if exceeding 2.0 dl / g, there is a problem of poor workability.

On the other hand, the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. If less than 1.5, the polymerization yield falls, and if it exceeds 2.5, there is a problem in that the moldability falls. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of palladium catalyst and polymerization temperature. That is, when the amount of the palladium catalyst increases or the polymerization temperature is 100 ° C. or more, the molecular weight distribution is increased.

On the other hand, the polyketone composition of the present invention is composed of an alloy consisting of a polyketone and polyalkylene carbonate combination, characterized in that to improve the long-term processing stability of the polyketone and improve the mechanical properties.

The weight of the polyalkylene carbonate is preferably 5 to 90% by weight based on the total weight, more preferably 30 to 70% by weight, still more preferably 10 to 20% by weight. When the content of the polyalkylene carbonate is less than 5% by weight, it may be difficult to impart a desired level of long-term processing stability due to the relative content decrease. When the content of the polyalkylene carbonate exceeds 90% by weight, mechanical properties such as tensile strength and impact strength may be excessively low. do. The polyalkylene carbonate is preferably one or two selected from the group consisting of polypropylene carbonate (PPC) and polyethylene carbonate (PEC), but is not limited thereto.

In addition, the polypropylene carbonate preferably has a number average molecular weight of 2,000 to 100,000, more preferably 2,500 to 55,000. The polyethylene carbonate preferably has a number average molecular weight of 100,000 to 300,000. As the polypropylene carbonate and the polyethylene carbonate each have the number average molecular weight, the alloy composition obtained therefrom may exhibit long-term processing stability. On the other hand, the polyketone alloy composition of the present invention as a result of the Hake Mixer (Haake Mixer) long-term residence evaluation at 220 ℃, 100rpm condition, it is preferable that the Max running time (Max running time) 300 minutes or more. This is because the machining stability is good in the running time of this range.

On the other hand, polyethylene carbonate (PEC) is an amorphous polymer included in polyalkylene carbonate, and has sticky property and biodegradability. In addition, oxygen permeability is better than that of nylon 6, and compatibility with polyketone, polylactic acid (PLA), polyvinyl chloride (PVC) and the like is good.

When the polyethylene carbonate is used as the polyalkylene carbonate, the weight may be 1 to 20 wt% based on the total weight, and more preferably 10 to 20 wt% based on the total weight. If the content of polyethylene carbonate is less than 1% by weight, it may be difficult to give a desired level of long-term processing stability due to the decrease in the relative content of polyethylene carbonate, and when it exceeds 20% by weight, the impact strength is greatly reduced.

In this case, the polyketone alloy composition may be a maximum running time of 140 minutes or more as a result of the Hake Mixer (Lake Mixer) long-term residence evaluation at 220 ℃, 100rpm conditions.

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

Method for producing a polyketone composition of the present invention comprises the steps of preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a double ligand compound of phosphorus; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone resin; And mixing the polyketone resin with polyalkylene carbonate to prepare a composition, but is not limited thereto.

Palladium acetate may be used as the palladium compound constituting the catalyst composition, and the amount of palladium acetate is preferably 10-3 to 10-1 mol, but is not limited thereto.

As the acid having a pKa value of 6 or less constituting the catalyst composition, one or more selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid, and sulfonic acid may be used, and preferably trifluoroacetic acid is used. 6-20 (mole) equivalent weight of the compound is appropriate.

Examples of the ligand ligands constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (e.g., 1,3-bis [di (2-methoxyphenylphosphino) propane), 1,3- Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane, ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis ( 1 selected from the group consisting of methylene)) bis (bis (2-methoxyphenyl) phosphine) and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine It is possible to use more than one species, and the amount of use thereof is 1 to 1.2 (mole) equivalents relative to the palladium compound.

The carbon monoxide, ethylene, and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer. The mixed solvent may be a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water. If the content of the water in the mixed solvent is less than 2 parts by weight of ketal may form a thermal stability during the process, if more than 10 parts by weight may lower the mechanical properties of the product.

In addition, the polymerization temperature is 50 ~ 100 ℃, the reaction pressure is suitable for the range of 40 ~ 60bar. The resulting polymer is recovered through polymerization and filtration and purification, 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 polyalkylene carbonate and then extruded by an extruder to finally obtain a polyketone composition. The blend may be prepared by melt kneading and extrusion into a twin screw extruder.

At this time, the extrusion temperature is 230 ~ 260 ℃, screw rotation speed is preferably in the range of 100 ~ 300rpm. If the extrusion temperature is less than 230 ℃ kneading may not occur properly, if it exceeds 260 ℃ may cause problems with the heat resistance of the resin. In addition, when the screw rotational speed is less than 100rpm it may not occur smooth kneading.

Hereinafter, the present invention will be described in detail through examples. However, these examples are only for the understanding of the present invention, and the scope of the present invention in any sense is not limited to these examples.

Example 1

Linear alternating polyketones consisting of carbon monoxide, ethylene and propene were produced from palladium acetate, trifluoroacetic acid and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine In the presence of the catalyst composition, the content of trifluoroacetic acid to palladium is 10-fold molar ratio, and is subjected to one step of polymerization temperature of 78 ° C. and two steps of 84 ° C. In the polyketone prepared above, carbon monoxide is 50 mol. %, Ethylene was 44 mol%, propylene was 6 mol%, and the melting point of the polyketone was 197 ° C., and the intrinsic viscosity (LVN) measured at 25 ° C. using hexa-fluoroisopropano (HFIP) was 2.2 dl / g. The terpolymer thus prepared is named M620A.

90 wt% of the prepared polyketone terpolymer and 10 wt% of polyethylene carbonate were prepared to prepare a composition, and the prepared composition was operated on an extruder by using a biaxial screw having a diameter of 40 cm and a L / D = 32 operating at 250 rpm. To pellets.

Example 2

Except for 80% by weight polyketone terpolymer, 20% by weight polyethylene carbonate is the same as in Example 1.

Comparative Example 1

Specimens were prepared in the same manner as in Example 1 except that 100 wt% polyketone was used.

Experimental Example 1: Cross over time (COT) measurement for processing stability evaluation

After preparing the prepared polyketone composition of the sample, and then injecting the COT specimen with a mini-injector, by measuring the COT (Cross Over Time, Gel point) through a rheometer {Physica MCR 301 of Anton Paar Co., Ltd. In comparison with the product of the comparative example, processing stability was evaluated, and the results are shown in Table 1 and FIG. 1. The gel point is determined by the time when G '= G ″ (sol-gel transition time point).

division	Resin composition	Cross over time (minutes)
Comparative Example 1	PK	25
Example 1	PK-PEC (90:10)	49
Example 2	PC-PEC (80:20)	37

PK: Polyketone (M620A), PEC: Polyethylene carbonate

As shown in Table 1, in the case of the Example, the cross-over time (COT) is increased compared to the comparative example, and thus, it seems that there is an effect of improving work stability (COT and processing stability is not clear, but the present work stability is represented by As one indicator).

Experimental Example 2: Haake Mixer Retention Evaluation for Evaluation of Work Stability

The prepared polyketone composition of Example was prepared as a specimen, and compared with the product of the comparative example, Haake Mixer retention evaluation was performed in the following manner to find work stability, and the results are shown in Table 2 and FIGS. 2 and 3.

Haake Mixer Long-term stay evaluation result: Introduce approximately 180g of sample while maintaining the jacket temperature of the outer chamber of the Haake mixer at 220 ℃, and measure the torque and temperature inside the chamber over time while rotating two rotors at a speed of 100rpm. do.

division	Resin composition	HaakeMax torque (Nm)	Haake Max running time (min)	HaakeTemp difference (max-default 220 ° C) (° C)
Comparative Example 1	PK	> 60 @ 115 minutes	125	40
Example 1	PK-PEC (90:10)	33 @ 135 minutes	145	25
Example 2	PK-PEC (80:20)	20 @ 45 minutes	> 180	20

PK: Polyketone (M620A), PEC: Polyethylene carbonate

As shown in Table 2, in the case of the embodiment, compared to the comparative example, the maximum torque value is small, the maximum running time is long, and even if the residence time is increased, it can be seen that the long-term processing stability is improved. In other words, Comparative Example 1 is completely decomposed after 120 minutes to lose fluidity, but the decomposition time is delayed due to the addition of polyethylene carbonate (PEC), even if the addition of 20% by weight (Example 2) exceeds 180 minutes It can be seen that the long-term processing stability in the extrusion process is improved by maintaining the stability.

Therefore, the polyketone composition prepared according to the present invention has excellent long-term processing stability and is suitable for application to injection and extrusion molding processes. have.

Experimental Example 3: Melt viscosity (MV) measurement for the evaluation of processing stability

The prepared polyketone composition of Example was prepared as a specimen, and then compared to the product of the comparative example, Melt viscosity was measured in the following manner to evaluate processing stability, and the results are shown in FIG. 4.

Predrying: 80 ℃, vacuum, overnight

Measuring temperature: 230 ℃

Die geometry: 30/1 mm

Sample melting time: 5 min

Shear rate: 100, 176, 267, 374, 556, 866, 1062, 1786, 2345, 4095, 7205, 12271 1 / s (12 points)

As shown in FIG. 4, the MV graphs of the examples and the comparative examples are almost similar, so that the melt viscosity is generally similar regardless of the amount of polyethylene carbonate added.

Experimental Example 4: Evaluation of Thermal Properties

The prepared polyketone composition of the above Example was prepared as a specimen, and then compared with the product of Comparative Example, the thermal properties were evaluated in the following manner, and the results are shown in Tables 3, 4 and 5.

-DSC was measured by the 1st, 2nd temperature rising and temperature-fall (-40 degreeC-240 degreeC from 20 degree-C / min) method, and Tm and Tc are the values at the time of secondary temperature rising and falling.

TGA was measured in a nitrogen atmosphere at 20 ° C./min from 40 ° C. to 850 ° C.

division	content(%)			DSC
	620A	PEC	Tg (℃)	Tm (℃)	ΔHm (J / g)	Tc (℃)	ΔHc (J / g)
Comparative Example 1	100	0	3.5	205.6	69.2	155.0	-74.0
Example 1	90	10	7.2	204.1	68.5	155.5	-76.8
Example 2	80	20	9.5	204.0	66.3	155.4	-67.9
-	0	100	10-15	-	-	-	-

	Td (℃, @ 5% decomposition)
division	content(%)		Td (℃)
	620A	PEC
Comparative Example 1	100	0	351
Example 1	90	10	338
Example 2	80	20	332
-	0	100	234

Experimental Example 5: Molecular Weight

After preparing the prepared polyketone composition of the sample to the specimen, the molecular weight was measured by the following method compared with the product of the comparative example, the results are shown in Table 5 and FIG.

Molecular weight is dissolved in Hexafluoroisopropanol (HFIP) solvent and measured by Gel Permeation Chromatography (GPC).

division	Sample	Mn	Mw	Mz	pdi
Comparative Example 1	PK (M620A) 100%	86,773	247,393	967,583	2.85
Example 1	PK / PEC (90:10)	73,242	220,851	855,184	3.02
Example 2	PK / PEC (80:20)	72,433	211,128	859,790	2.91
-	PEC 100%	71,782	156,423	295,724	2.18

Experimental Example 6: Evaluation of Mechanical Properties

The prepared polyketone composition of the Example was prepared as a specimen, and then compared with the product of the comparative example, the mechanical properties were evaluated in the following manner, and the results are shown in Table 6 and FIG. 7.

1. Extruded with 40mm extruder compounding center.

2. Tensile strength: It was performed according to ASTM D638.

3. Impact strength: It was carried out under the conditions of room temperature [24] ℃ according to ASTM D256.

4. Melt Index: Measured by 2.16 kg load at 240 ° C. according to ASTM D1238, expressed as weight (g) of polymer melted for 10 minutes.

5. Elongation: It was performed according to ASTM D638 as tensile strength.

6. Flexural modulus and flexural strength: Performed according to ASTM D790.

division	content(%)		Tensile Strength (MPa)	% Elongation	Flexural modulus (Mpa)	Flexural Strength (Mpa)	Impact strength (kJ / m2)	MI (g / 10min)
	620A	PEC
Comparative Example 1	100	0	61	648	1096	49	14.2 (14.9 / 14.0 / 13.6)	5.2
Example 1	90	10	58	637	938	42	11.5 (12.3 / 3.7 / 9.1 / 14.6 / 13.0) **	5.6
Example 2	80	20	53	626	772	35	3.6 (6.2 / 3.6 / 3.7 / 3.6 / 3.5)	6.3

As shown in Table 6, as the PEC is added, the melt index (MI) increases, and the tensile strength, the flexural modulus, and the impact strength decrease. In particular, since the impact drop is large when 20 wt% of PEC is added, it is not advantageous to add more than 20 wt% of PEC in terms of impact.

Experimental Example 7: Color

The prepared polyketone composition of the above Example was prepared as a specimen, the color was evaluated by the following method in comparison with the product of the comparative example, the results are shown in Table 7 and FIG.

-The color difference was measured by ASTM E313-00 method for Yellow Index (YI) and L, a, b values by CIE L * a * b (CIELAB) method.

division	Furtherance (%)		Color difference
	620A	PEC	YI	L	a	b
Comparative Example 1	100	0	23	55.0	-1.6	8.9
Example 1	90	10	21	72.7	-0.9	9.4
Example 2	80	20	17	76.6	-0.3	8.0

As shown in Table 7, it can be seen that the YI value is slightly improved according to the addition of PEC, and in particular, the L value is greatly increased.

Example 3

Linear alternating polyketones consisting of carbon monoxide, ethylene and propene were produced from palladium acetate, trifluoroacetic acid and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine In the presence of the catalyst composition, the content of trifluoroacetic acid to palladium is 10-fold molar ratio, and is subjected to one step of polymerization temperature of 78 ° C. and two steps of 84 ° C. In the polyketone prepared above, carbon monoxide is 50 mol. %, Ethylene is 46 mol%, propylene is 4 mol% The melting point of the polyketone is 220 ° C., the molecular weight measured by GPC (Gel Permeation Chromatography) is Mn = 52,500, Mw = 141,400, molecular weight dispersion PDI = 2.69 The terpolymer thus prepared is named M330A.

90 wt% of the prepared polyketone terpolymer (M330A) and 10 wt% of polypropylene carbonate (PPC, manufactured by Aldrich Co., Ltd.) were prepared to prepare a composition, and the prepared composition was 40 cm in diameter operating at 250 rpm, and L / D. The pellets were prepared on an extruder using a biaxial screw of = 32. The molecular weight of PPC used was Mn = 51,000, Mw = 149,000 and PDI = 2.9.

Example 4

Except that 80% by weight of polyketone terpolymer M330A, 20% by weight of polypropylene carbonate was the same as in Example 3.

Example 5

Except for adding 70% by weight of polyketone terpolymer M330A, 30% by weight of polypropylene carbonate was the same as in Example 3.

Example 6

Except that 50% by weight of polyketone terpolymer M330A, 50% by weight of polypropylene carbonate was the same as in Example 3.

Example 7

It is the same as Example 3 except adding 30 weight% of polyketone terpolymer M330A and 70 weight% of polypropylene carbonate.

Example 8

Except that 20% by weight of polyketone terpolymer M330A, 80% by weight of polypropylene carbonate was the same as in Example 3.

Example 9

Except that 10% by weight of polyketone terpolymer M330A, 90% by weight of polypropylene carbonate was the same as in Example 3.

Example 10

95% by weight of polyketone terpolymer M330A and 5% by weight of polypropylene carbonate were added thereto, and the same procedure as in Example 3 was carried out except that the molecular weight of the used PPC was Mn = 2,900, Mw = 5,500 and PDI = 1.9.

Example 11

Except for adding 90% by weight of polyketone terpolymer M330A, 10% by weight of polypropylene carbonate was the same as in Example 10.

Example 12

Except for adding 90% by weight of polyketone terpolymer M330A, 10% by weight of polyethylene carbonate was the same as in Example 3. The number average molecular weight of the used PEC is 200,000.

Example 13

Except that 80% by weight of polyketone terpolymer M330A, 20% by weight of polyethylene carbonate was the same as in Example 3. The number average molecular weight of the used PEC is 200,000.

Comparative Example 2

Example 13 A specimen was prepared in the same manner as in Example 13 except 100 wt% of polyketone M330A was used.

Property evaluation

The physical properties of the specimens prepared in Examples 3 to 13 and Comparative Example 2 were evaluated, and the results are shown in Tables 8 and 9 below.

division	330A	PPC		PEC	Tensile Strength (MPa)	% Elongation		Flexural Strength (MPa)	Flexural Modulus (MPa)	Charpy Impact Strength (kJ / m2)	MI (g / 10min)
		Mn 51000	Mn 2900			surrender	Breaking
Comparative Example 2	100	-	-	-	59.1	-	14	57.1	1,465	6.6	58
Example 3	90	10	-	-	50.2	18	45	54	1,364	6.1	57
Example 4	80	20	-	-	44.8	17	30	45.1	1,098	4.2	62
Example 5	70	30	-	-	36.8	16	21	35.2	842	3.1	-
Example 6	50	50	-	-	22.7	15	24	18.6	448	3.2	109
Example 7	30	70	-	-	13.3	5	18	4.7	115	2.1	-
Example 8	20	80	-	-	10.5	4	32	2.8	77	1.1	148
Example 9	10	90	-	-	7.5	2	25	1.0	19	1.4	-
Example 10	95	-	5	-	46.4	14	18	61.1	1,655	8.4	-
Example 11	90	-	10	-	41.1	-	12	48.2	1,187	9.2	253
Example 12	90	-	-	10	49.8	20	40	48.5	1,180	5.3	56
Example 13	80	-	-	20	42.0	20	76	41.5	980	3.6	63

PK: Polyketone (M330A, Hyosung), PPC: Polypropylene carbonate (Aldrich), PEC: Polyethylene carbonate (LG Chemical)

As shown in Table 8, in the case of Examples 3 to 9, the flexural modulus is reduced compared to the comparative example to improve flexibility, and in the case of PPC having a large number average molecular weight, the MI value increases as the content is increased and the fluidity is increased. This was evaluated as an improvement. In addition, in the case of Examples 10 and 11 was evaluated that the impact strength is improved when the number average molecular weight of the PPC is small, the mechanical properties can be adjusted according to the molecular weight control of the added PPC. In addition, in Examples 12 and 13, as the PEC content is increased, the bending modulus decreases, the fluidity is improved, and the impact strength decreases.

division	330A	PPC (Mn 51000)	PPC (Mn 2900)	PEC	HaakeMax torque (Nm)	HaakeMax running time (min)	Haake Temp difference (℃) (max- initial value 220 ℃)
Comparative Example 2	100	-	-	-	> 60 @ 160 minutes	175	37
Example 3	90	10	-	-	19 @ 300 minutes	> 300	12
Example 11	90	-	10	-	16 @ 157 minutes	195	13
Example 12	90	-	-	10	23 @ 300 minutes	> 300	24
Example 13	80	-	-	20	15 @ 300 minutes	> 300	15

As shown in Table 9, in the case of Examples 3, 12 and 13, the maximum torque value is smaller, the Max running time is longer than the comparative example, and the temperature change is small even if the residence time is increased. This was evaluated to be improved. In other words, Comparative Example 2 is completely decomposed after 175 minutes and loses fluidity, but in the case of Example 3 in which polypropylene carbonate (PPC) was added and in Examples 12 and 13 in which polyethylene carbonate (PEC) was added In this case, it can be seen that the processing stability in the extrusion process is improved by maintaining stability without losing fluidity even after 300 minutes.

Therefore, the polyketone composition prepared in Examples rather than Comparative Examples was evaluated to be suitable for use as tubes, pipes, food packaging films, general injection parts, while improving mechanical stability while improving processing stability. In particular, the alloy composition applied to PPC or PEC 50% or more is suitable for use as a flexible and environmentally friendly flooring sheet with a flex modulus of 500 MPa or less.

Claims (8)

1. A polyketone copolymer composed of repeating units represented by the following formulas (1) and (2), characterized in that it comprises a linear alternating polyketone and polyalkylene carbonate having y / x of 0.03 to 0.3 Polyketone Alloy Composition.

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

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

   (x, y represents the mole% of each of the general formulas (1) and (2) in the polymer)
2. The method of claim 1,

   The polyalkylene carbonate is a polyketone alloy composition, characterized in that one or two selected from the group consisting of polypropylene carbonate (PPC; Polypropylene carbonate) and polyethylene carbonate (PEC; Polyethylene carbonate).
3. The method of claim 2,

   The number average molecular weight of the polypropylene carbonate is 2,000 to 100,000, the polyketone alloy composition, characterized in that the number average molecular weight of the polyethylene carbonate is 100,000 to 300,000.
4. The method of claim 1,

   The composition ratio of the polyalkylene carbonate is a polyketone alloy composition, characterized in that 5 to 90% by weight relative to the total polyketone alloy composition.
5. The method of claim 4, wherein

   Polyketone alloy composition, characterized in that the maximum running time (max running time) of 300 minutes or more as a result of the Hake Mixer (Haake Mixer) long term evaluation at 220 ℃, 100rpm conditions of the polyketone alloy composition.
6. The method of claim 1,

   The polyalkylene carbonate is polyethylene carbonate, the composition ratio of the polyethylene carbonate relative to the total weight of the polyketone alloy composition is 1 to 20% by weight polyketone alloy composition.
7. The method of claim 6,

   The polyketone composition, characterized in that the maximum running time (max running time) of 140 minutes or more as a result of the Hake Mixer (Haake Mixer) long term evaluation at 220 ℃, 100rpm conditions of the polyketone alloy composition.
8. The method of claim 1,

   The ligand of the catalyst composition used in the polyketone polymerization is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine And (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine). The polyketone alloy composition according to claim 1, wherein the polyketone alloy composition is one or two selected from the group consisting of

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