KR102011912B1 - High impact polyketone alloy resin composition with improved flexibility and heat resistance - Google Patents

Abstract

The present invention provides a high impact heat resistant polyketone composition with improved flexibility, comprising linear alternating polyketones and thermoplastic polyurethanes consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon.
The high-impact heat-resistant polyketone composition with improved flexibility of the present invention can help to improve the physical properties of the product and the stability of the processing process when applied to special parts requiring impact resistance and pressure resistance characteristics, and various industries such as automotive, electrical / electronics, etc. When applied as a material, the quality of the product can be improved.

Description

High impact polyketone alloy resin composition with improved flexibility and heat resistance

The present invention relates to a high-impact heat-resistant polyketone alloy resin composition with improved flexibility, in detail by adding a thermoplastic polyurethane (TPU; Themoplastic Polyurethane) to the polyketone, while maintaining the advantages of the existing high-impact heat-resistant polyketone resin The present invention relates to a polyketone composition having improved flexibility.

Polyketone (PK) has a lower raw material and polymerization process cost than 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. It is widely applied.

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 preparing polyketone polymers is usually a compound of Group VIII metal selected from palladium, cobalt or nickel, and anions of non-hydro halogen strong-hydrohalogentic acid. Catalyst compositions produced from bidentate ligands of phosphorus, arsenic or antimones are used.

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.

The existing high-impact heat-resistant polyketone alloy resin is excellent in heat resistance and can be applied to parts requiring high temperature heat resistance such as automobile parts. However, if the pressure-resistant process is included in the insert part of the manufacturing process of the finished product, high flexibility is required for each component to prevent damage to the product, and the conventional high-impact heat-resistant polyketone material alone has a disadvantage of lack of flexibility.

The present invention is to solve the above problems by adding a thermoplastic polyurethane (TPU; Themoplastic Polyurethane) excellent in fluidity and flexibility to the polyketone to improve the flexibility that was lacking while maintaining the advantages of the existing high-impact heat-resistant polyketone resin It is an object to provide a polyketone composition.

In order to achieve the above technical problem, the present invention is a polyketone composition comprising 60 to 70 parts by weight of linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon and 1 to 5 parts by weight of thermoplastic polyurethane. To provide a means for solving the above problems.

The polyketone composition may further include 15 to 20 parts by weight of polyamide (PA6) and 10 to 15 parts by weight of ethylene octene rubber (EOR) in addition to the polyketone and the thermoplastic polyurethane. In addition, the polyketone composition may further comprise 0.1 to 0.5 parts by weight of copper oxide (CuO) and 0.2 to 1 parts by weight of silicone oil in addition to the polyketone and thermoplastic polyurethane.

In the polyketone composition of the present invention, the retention rate of tensile strength measured after aging for 6 weeks in an oven maintained at 145 ° C relative to the initial tensile strength is 85 to 95%, and the retention of impact strength is 18 to 25%. It features.

In addition, the present invention provides a harness connector for a polyketone automobile manufactured using the polyketone composition.

The high-impact heat-resistant polyketone composition with improved flexibility of the present invention can be applied to various industrial materials such as automobiles, electrical / electronics fields, and especially to special parts requiring impact resistance and pressure resistance characteristics to improve product properties and stability of processing processes. Can be helpful.

EMBODIMENT OF THE INVENTION Hereinafter, although the best form for implementing this invention is demonstrated in detail, this invention is not limited to these.

The present invention is characterized by providing a high-impact heat-resistant polyketone composition having improved flexibility by adding thermoplastic polyurethane (TPU) to the polyketone.

First, the poly ketone resin used in the present invention is an engineering plastic and a recently developed new resin, which has excellent mechanical properties and molding properties such as impact strength, and is usefully applied as a material for various molded products or parts. It is a synthetic resin. 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 a low moisture hygroscopicity compared to polyamide material, so it is possible to design various products with little change in dimensions and physical properties due to moisture absorption, and polyketone resin has a low density compared to aluminum material, which is suitable for product weight reduction. In particular, polyketone is a material having a stronger molecular bond than polyethylene, and the melting temperature is about 100 ° C. higher than that of polyethylene, and is a material having superior strength and heat resistance stability to polyethylene.

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 preparing polyketone by terpolymerization of ethylenic and propylene unsaturated compounds, the carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer. As an example of the solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of the water in the mixed solvent is less than 2 parts by weight of ketal may be formed, the heat stability during the process may be lowered, if more than 10 parts by weight may lower the mechanical properties of the product. As a preferable example of the mixed solvent, a mixed solvent consisting of 70 to 90% by volume acetic acid and 10 to 30% by volume of water can be used as a liquid medium, and can be prepared by adding benzophenone during polymerization. In the case where a mixed solvent consisting of acetic acid and water is used without using methanol, dichloromethane, or nitromethane, which have been used mainly for the production of polyketone as a liquid medium, it is possible to improve the catalytic activity while reducing the production cost of polyketone. It has an excellent effect. 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 catalyst activity is less affected. However, when the concentration is more than 10% by volume, the catalytic activity increases rapidly. 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 the mixed solvent which consists of 70-90 volume% acetic acid and 10-30 volume% water as a 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 acetylacetate, 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, trifluoro copper acetate, 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) in terms of yield and molecular weight of polyketone are palladium compounds, and in terms of catalytic activity and intrinsic viscosity improvement. 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 expression equivalent to 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, known to have the highest activity in the polymerization catalyst The structure is simpler and has a lower molecular weight. As a result, the present invention can provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst in the art while further reducing the production cost and cost thereof. The method for producing 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 ligand preparation method for the 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 synthesized in bulk.

In a preferred embodiment, the method for preparing a ligand for a polyketone polymerization catalyst is (a) adding bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) to a reaction vessel under a nitrogen atmosphere and sodium hydride at room temperature. Adding 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, 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 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.

On the other hand, 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 (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine ligand can be synthesized through the following four steps. Nate and 1,5-dibromopentane are boiled under sodium ethoxide and ethanol, and then reduced under lithium aluminum hydride and tetrahydrofuran to synthesize 1,1-cyclohexanedimethanol, and tosyl chloride and pyridine. It can be reacted under to give a leaving group, which is reacted under 2-methoxyphenylphosphine, sodium hydride and dimethyl sulfoxide to obtain the ligand. Purification steps such as graphy and recrystallization, and purity of each step can be confirmed by nuclear magnetic resonance analysis.

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) used is generally in the range thereof because 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 from 0.01 to 100 mmol, preferably from 0.01 to 10 mmol, per liter of 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, benzophenone may be added during the polymerization of the polyketone. By adding benzophenone during the polymerization of the polyketone, the effect of improving the intrinsic viscosity of the polyketone can be achieved. 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, the ratio of carbon monoxide and ethylenically unsaturated compound is generally 1: 1. However, when a mixed solvent of acetic acid and water is used as a liquid medium and benzophenone is added during polymerization, carbon monoxide and ethylenically unsaturated compound are used. When the ratio of 1 to 1 to 2 and propylene is adjusted to 1 to 20 mol% relative to the total mixed gas, not only the workability is improved but also the catalytic activity and the intrinsic viscosity can be simultaneously achieved. If the amount of propylene is less than 1 mol%, the effect of terpolymerization 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. It is desirable to.

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 olefinically unsaturated compounds are added to increase the catalytic activity and intrinsic viscosity of the polyketone. In addition to being improved, 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.

The present invention may further include conventionally known additives such as antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants, and other materials to improve processability and physical properties of the polymer.

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. 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.

As mentioned above, polyketone is manufactured according to the above manufacturing process.

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 the polyketone terpolymer is used as the main polymer component of the composition of the present invention, for each unit containing the second hydrocarbon moiety in the terpolymer, there are at least two or more units containing the ethylene moiety, and It is preferable that there are 10-100 units containing the hydrocarbon part of 2.

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 the following 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. And y / x is more preferably 0.03 to 0.1.

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

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

In addition, the melting point of the polymer may be controlled by controlling the ratio of ethylene and propylene of the polyketone polymer. In one example, the melting point is about 220 ° C. when the molar ratio of ethylene: propylene: carbon monoxide is adjusted to 46: 4: 50, but the melting point is adjusted to 235 ° C. when the molar ratio is adjusted to 47.3: 2.7: 50.

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, whether the polymer is copolymer or terpolymer, and in the case of the terpolymer, the properties 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 25 ° C. using a standard tubular viscosity measuring device and HFIP (Hexafluoroisopropanol) is 0.5 dl / g to 10 dl / g, preferably 0.8 dl / g to 4 dl / g. Preferably it may be 1.0dl / g ~ 2.0dl / g. At this time, when the limiting viscosity number is less than 0.5dl / g, the mechanical properties are inferior, when it exceeds 10dl / g, there is a problem that the workability is inferior. In the present invention, polyketone having an intrinsic viscosity number of 1.0 dl / g to 2.0 dl / g is most preferable in terms of mechanical properties and processability.

Meanwhile, the molecular weight distribution of the polyketone may be 1.5 to 2.5, more preferably 1.8 to 2.2. If the molecular weight distribution is less than 1.5, the polymerization yield falls, and if it exceeds 2.5, there is a problem in inferior moldability. In order to control the molecular weight distribution, it is possible to adjust according to the amount of the palladium catalyst and / or 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.

The polyketone of the present invention preferably has a content of palladium element of 50 ppm or less. When the content of the palladium element exceeds 50 ppm, thermal denaturation and chemical denaturation due to the remaining palladium element are likely to occur, and during melt molding, a phenomenon such as an increase in melt viscosity and an increase in dopant viscosity when dissolved in a solvent occurs. , Workability becomes poor. In addition, since a large amount of palladium elements remain in the polyketone molded body obtained after molding, the heat resistance of the molded body is deteriorated. The smaller the content of the palladium element in the polyketone from the viewpoint of process passability and the heat resistance of the molded product, the more preferable. The content is more preferably 10 ppm or less, still more preferably 5 ppm or less, and most preferably 0 ppm.

Specifically, the polyketone composition according to the embodiments of the present invention is composed of an alloy including a combination of polyketone and thermoplastic polyurethane (TPU), and maintains the advantages of the existing high-impact heat-resistant polyketone resin while maintaining flexibility. It is characterized by improving.

Thermoplastic polyurethane is a generic term for high molecular compounds having a urethane bond (-NH-COO) in the molecule, and is generally produced by addition reaction using polyisocyanate and polyol as main ingredients. Polyurethane has a wide variety of raw materials, and according to their combination method, it is possible to synthesize polyurethane materials with various molecular structures and physical properties. Typically, polyester type and polyether type Divided by) Both polyester series and polyether series include urethane groups in the polymer chain, so that the polyesters and polyethers that can be used in the present invention are not limited, but in terms of flexibility, the free volume between molecular chains can be further increased. It may be more advantageous to use polyester series polyurethane resins.

The thermoplastic polyurethane is a material having excellent compatibility with polyketones and excellent fluidity and flexibility. The polyketone composition of the present invention preferably contains 1 to 5 parts by weight of thermoplastic TPU based on 60 to 70 parts by weight of polyketone. Do. When the content of the TPU is less than 1 part by weight, the effect of improving flexibility is insignificant, and when the content of the TPU is more than 5 parts by weight, a decrease in mechanical properties may occur, such as a decrease in tensile strength.

In addition, the polyketone composition is 15 to 20 parts by weight of polyamide (PA6), preferably 17 to 18 parts by weight and ethylene octene rubber, based on 60 to 70 parts by weight of polyketone and 1 to 5 parts by weight of thermoplastic polyurethane. (EOR; Ethylene-Octene Rubber) may further include 10 to 15 parts by weight, preferably 12 to 13 parts by weight.

Since polyamide is capable of hydrogen bonding between -NH in a polyamide chain and -CO group in a polyketone when mixed with polyketone, polyamide is a material having excellent compatibility with polyketone. In addition, when mixed with the modified rubber, the -NH ₂ group at the end of the polyamide chain can be combined with the maleic anhydride portion of the modified rubber, so that the compatibility with the modified rubber is also excellent. Thus, by mixing the polyamide in the polyketone composition of the present invention, the compatibility of the polyketone and rubber is enhanced, through which the impact strength of the polyketone can be significantly improved. If the content of the polyamide is less than 15 parts by weight, the compatibility improvement effect may be insignificant, and if it exceeds 20 parts by weight, mechanical properties may be reduced.

Ethylene octene rubber is a rubber for impact reinforcement, by mixing the ethylene octene rubber in the polyketone composition of the present invention, not only the impact strength is improved but also the physical property retention rate when exposed to heat for a long time. Ethylene octene rubber is a elastomer that is considerably smaller in stress than polyketone resin and polyamide. When the content of ethylene octene rubber is less than 10 parts by weight, the effect of improving impact strength and long-term thermal stability may be insignificant. If exceeded, mechanical properties may be reduced.

When the content of the polyamide and the ethylene octene rubber is within the above range, the impact strength of the polyketone composition is maintained in the state where the overall mechanical properties are not largely reduced.

In addition, the polyketone composition may further include 0.1 to 0.5 parts by weight of copper oxide (CuO) and 0.2 to 1 parts by weight of silicone oil based on 60 to 70 parts by weight of polyketone and 1 to 5 parts by weight of thermoplastic polyurethane.

CuO acts as a metal heat-resistant agent, if the content is less than 0.1 parts by weight, the effect of improving heat resistance is insignificant, and if it exceeds 0.5 parts by weight, the viscosity is increased, the processing stability is lowered, the manufacturing cost is increased and the surface properties may be reduced.

Silicone oil acts as an impact reinforcing material, if the content is less than 0.2 parts by weight it is not possible to obtain the effect of sufficient impact reinforcement, if it exceeds 1 part by weight it is not preferable because only the manufacturing cost can be increased without gain in mechanical properties.

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 (polymerization solvent); Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and a mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone resin; Preparing a polyketone composition by mixing 60 to 70 parts by weight of the polyketone resin and 1 to 5 parts by weight of the thermoplastic polyurethane; And extruding / injecting the composition to prepare pellets, but is not limited thereto. Additionally, the polyketone resin and the thermoplastic polyurethane may be mixed with 15 to 20 parts by weight of polyamide (PA6) and 10 to 15 parts by weight of ethylene octene rubber, and 0.1 to 0.5 parts by weight of copper oxide (CuO) and 0.2 parts by weight of silicone oil. To 1 part by weight may be prepared by further mixing.

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 moles, 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-phase polymerized in a mixed solvent to produce a linear terpolymer. As one embodiment of 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 the water in the mixed solvent is less than 2 parts by weight of the ketal may be formed to reduce the heat resistance during the process, if more than 10 parts by weight may lower the mechanical properties of the product.

In addition, the reaction temperature is 50 ~ 100 ℃ during the polymerization, the reaction pressure is in the range of 40 ~ 60bar is appropriate. 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.

A thermoplastic polyurethane is blended with the obtained polyketone to prepare a composition. At this time, the preferred composition ratio of the polyketone is 60 to 70 parts by weight, and 1 to 5 parts by weight of the thermoplastic polyurethane. 15 to 20 parts by weight of polyamide (PA6) and 10 to 15 parts by weight of ethylene octene rubber may be additionally mixed, and 0.1 to 0.5 parts by weight of copper oxide (CuO) and 0.2 to 1 part by weight of silicone oil may be further mixed. have. The composition may be prepared by melt kneading and extruding by feeding 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, if the screw rotational speed is less than 100rpm it may not occur smooth kneading.

The present invention is a retention rate of the tensile strength measured after aging for 6 weeks in an oven maintained at 145 ℃ compared to the initial tensile strength of the polyketone composition through the composition and manufacturing method as described above is 85 to 95%, impact strength The retention rate of 18 to 25% may exhibit an excellent long-term heat stability.

Generally, there are many electric wires for power supply and signal transmission to a lamp and a control device in a vehicle, and harness is a general term for wires for electric and electronic devices in such a vehicle. It is almost essential in a relatively small car, etc., and long-term heat resistance is required in order to be able to use it for a long time in an in-car environment. Therefore, the polyketone composition excellent in long-term heat stability produced by the present invention can be applied to the harness connector for automobiles.

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 46 mol%, propylene was 4 mol%, and the melting point of the polyketone was 220 ° C., and the melt index measured under a load of 240 ° C. and 2.16 kg was 50 to 80 g / 10 min.

68.25% by weight of the prepared polyketone terpolymer, 17% by weight of polyamide (PA6, Hyosung 1011BRT), 13% by weight of ethylene octene rubber (N493D, Dupont), 0.25% by weight of copper oxide (CuO), 0.5% by weight of silicone oil And 1 wt% thermoplastic polyurethane (product of BASF 785A) to prepare a composition, and the prepared composition was pelleted onto an extruder on a extruder using a biaxial screw with L / D = 32 operating at 250 rpm. Prepared.

Example 2

Specimens were prepared in the same manner as in Example 1, except that 67.25 wt% of polyketone terpolymer and 2 wt% of thermoplastic polyurethane were added thereto.

Example 3

A specimen was prepared in the same manner as in Example 1, except that 64.25% by weight of polyketone terpolymer and 5% by weight of thermoplastic polyurethane were added.

Comparative Example 1

69.25% by weight of polyketone terpolymer was added, and the specimen was prepared in the same manner as in Example 1 except that thermoplastic polyurethane was not added.

Property evaluation

Physical properties of the specimens prepared in Examples 1 to 3 and Comparative Example 1 before and after aging for 6 weeks in a 145 ° C convection oven were measured according to the following method, and initial flexural strength. The flexural modulus is shown in Table 1, the tensile strength and its retention rate in Table 2, and the impact strength and its retention rate in Table 3.

1. Tensile strength: It was conducted according to ISO 527.

2. Notched Charpy: Implemented according to ISO 179.

3. Flexural strength: conducted according to ISO 178.

division Flexural strength
(MPa) Flexural modulus
(MPa) Comparative Example 1 47 1283 Example 1 42 963 Example 2 37 880 Example 3 31 765

division Tensile Strength (MPa) Retention rate
(%) 0 days 10 days 20 days 30 days 42 days Comparative Example 1 44 37 39 40 37 83 Example 1 42 36 38 39 39 92 Example 2 37 34 33 33 33 89 Example 3 30 26 27 25 26 87

division Impact Strength (kJ / m ² )
Retention rate
(%) 0 days 10 days 20 days 30 days 42 days Comparative Example 1 58 12 11 14 12 21 Example 1 68 15 15 14 14 21 Example 2 78 20 17 16 15 19 Example 3 82 20 13 15 15 18

As shown in Table 1 and 2, in the case of the embodiment of the present invention it was shown that the tensile strength retention is excellent when the aging for 6 weeks in the 145 ℃ oven, compared to the comparative example, the flexural modulus (Modulus) is reduced flexibility It can be seen that the (flexibility) is improved. Therefore, the high-impact and heat-resistant polyketone composition with improved flexibility manufactured through the embodiment of the present invention is suitable for various industrial materials such as automobiles, electrical / electronics fields, and especially when applied as a special component requiring impact resistance and pressure resistance characteristics. It can improve the physical properties and processing stability.

Claims (5)

60 to 70 parts by weight of linear alternating polyketones consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon;
1 to 5 parts by weight of thermoplastic polyurethane;
15 to 20 parts by weight of polyamide (PA6);
10 to 15 parts by weight of ethylene octene rubber;
0.1 to 0.5 parts by weight of copper oxide (CuO); And
It contains 0.2 to 1 parts by weight of silicone oil,
Polyketone composition, characterized in that the retention of tensile strength measured after aging for 6 weeks in an oven maintained at 145 ℃ relative to the initial tensile strength is 85 to 95%, the retention of impact strength is 18 to 25%.
delete delete delete An automobile harness connector made of the polyketone composition of claim 1.