KR101956626B1 - Glass Fiber reinforced Polyketone resin composition having improved surface appearance - Google Patents

Glass Fiber reinforced Polyketone resin composition having improved surface appearance Download PDF

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KR101956626B1
KR101956626B1 KR1020170078155A KR20170078155A KR101956626B1 KR 101956626 B1 KR101956626 B1 KR 101956626B1 KR 1020170078155 A KR1020170078155 A KR 1020170078155A KR 20170078155 A KR20170078155 A KR 20170078155A KR 101956626 B1 KR101956626 B1 KR 101956626B1
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polyketone
bis
surface appearance
weight
composition
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KR20180138271A (en
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정재호
김중인
정진주
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효성화학 주식회사
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/043Reinforcing macromolecular compounds with loose or coherent fibrous material with glass fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/05Alcohols; Metal alcoholates
    • C08K5/053Polyhydroxylic alcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/14Peroxides
    • EFIXED CONSTRUCTIONS
    • E03WATER SUPPLY; SEWERAGE
    • E03BINSTALLATIONS OR METHODS FOR OBTAINING, COLLECTING, OR DISTRIBUTING WATER
    • E03B7/00Water main or service pipe systems
    • E03B7/09Component parts or accessories
    • E03B7/095Component holders or housings, e.g. boundary boxes
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01FMEASURING VOLUME, VOLUME FLOW, MASS FLOW OR LIQUID LEVEL; METERING BY VOLUME
    • G01F15/00Details of, or accessories for, apparatus of the preceding groups insofar as such details or appliances are not adapted to particular types of such apparatus
    • G01F15/10Preventing damage by freezing or excess pressure or insufficient pressure

Abstract

The present invention relates to a polyketone composition having improved surface appearance, which comprises a C2-C20 polyhydric alcohol capable of hydrogen bonding to a linear alternating polyketone composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon and glass fibers .
The present invention is characterized in that a C2 to C20 polyhydric alcohol is applied to a polyketone to lower the crystallization temperature and crystallinity of the polyketone, and the decrease in the crystallization temperature and crystallinity is due to the improvement in surface appearance.

Description

[0001] The present invention relates to a fiber reinforced polyketone resin composition having improved surface appearance,

The present invention relates to a polyketone resin composition having improved surface appearance, and more particularly, to a polyketone resin composition having a surface appearance in which a C2-C20 polyhydric alcohol capable of hydrogen bonding with a polyketone is introduced into a glass fiber- To a polyketone resin composition.

Thermoplastic polymers are predominantly processed in molten state. No polymer is resistant to changes associated with structure and state without any change in its chemical structure. Cross-linking, oxidation, molecular weight changes, and consequent changes in physical and industrial properties can also result. To reduce the stresses on the polymers during processing, different additives are added according to the polymer.

Different additives are often used at the same time, each of which takes on a particular task. For example, antioxidants and stabilizers can be used to allow the polymer to withstand processing without chemical damage and then to have stability for external effects such as heat, UV light, weathering, and oxygen (air) Is used. In addition to improved flow properties, the lubricant prevents the polymer melt from being excessively attached to high temperature mechanical parts and acts as a dispersant for pigments, fillers and reinforcing agents.

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

The polyketone having the above characteristics can be produced by reacting carbon monoxide (CO) and an olefin such as ethylene or propylene as a catalyst with a transition metal complex such as palladium (Pd) or nickel (Ni) It is already known that carbon monoxide and olefin are obtained by alternately bonding with each other by using a polymerization initiator (Industrial Materials, December, 5, 1997). On the other hand, there is a growing interest in a family of linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, known as polyketones or polyketone polymers. U.S. Patent No. 4,880,903 discloses a linear alternating polyketone terpolymer consisting of carbon monoxide, ethylene and terephthalic unsaturated hydrocarbons such as propylene.

The process for preparing the polyketone polymer is generally carried out by reacting a compound of a Group VIII metal selected from among palladium, cobalt or nickel with an anion of a strong halogen-hydrohalogentic acid, , Phosphorus, arsenic, or antimony (Antimon).

U.S. Patent No. 4,843,144 discloses a method for producing a polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of a nonhydrohalogen acid having a pKa of less than 6, and a catalyst that is a bidentate ligand Lt; / RTI >

On the other hand, in order to improve the physical properties such as the improvement of the mechanical strength of polyketone, a method of adding glass fiber or the like is used. In order to improve the physical properties of the glass fiber, a large amount of the glass fiber should be added. there is a problem that flow mark is generated and appearance becomes poor, and thus there is a need for a polyketone composition having improved surface characteristics. Accordingly, the present inventors have found that the polyketone resin is improved in thermal characteristics (crystallization temperature and crystallinity) of the polyketone resin by introducing a C2-C20 polyhydric alcohol capable of hydrogen bonding to the polyketone resin, Thereby completing the invention.

In order to solve the above-mentioned problems, the present invention provides a polyketone which can improve the thermal characteristics (crystallization temperature and crystallinity) of a polyketone by introducing a C2-C20 polyhydric alcohol capable of hydrogen bonding to the polyketone, And to provide a polyketone composition containing the same.

In order to accomplish the above object, the present invention provides a method for producing a polyolefin composition, which comprises a linear alternating polyketone composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon, a C2-C20 polyhydric alcohol and a glass fiber capable of hydrogen bonding, And provides an improved polyketone resin composition.

The polyhydric alcohol is one or more selected from the group consisting of ethylene glycol, glycerol, pentaerythritol, sorbitol and dipentaerythritol, , And the ratio of the polyketone to the polyhydric alcohol is 80 to 97 parts by weight: 3 to 20 parts by weight.

On the other hand, the polyketone composition is characterized in that the content of reinforcing fibers is 20 to 60% by weight based on the total weight of the polyketone composition, and the crystallization temperature (DSC) has a crystallization temperature of 150 to 175 ° C and a crystallinity of 10 to 35% .

Also provided is a metering outer shell made using the polyketone composition.

In the present invention, by introducing a C2 to C20 polyhydric alcohol into a polyketone, a crystallization temperature and a degree of crystallization are lowered, and the crystallization temperature and the degree of crystallization are lowered to improve the surface appearance of the polyketone composition.

The polyketone composition improved in surface appearance of the present invention can improve the surface while simultaneously improving physical properties such as mechanical strength while maintaining excellent flow properties and is also applicable to control the physical properties in the synthesis of polyketone and other resins There is an advantage to be able to.

Fig. 1 is a flow mark judgment standard for judging the degree of surface appearance improvement. O means that the surface appearance is good,? Means that the surface appearance is normal, and X means that the surface appearance is bad.

Hereinafter, the present invention will be described in detail.

The present invention is characterized by providing a polyketone composition improved in surface appearance by adding a C2-C20 polyhydric alcohol and glass fiber capable of hydrogen bonding to polyketone.

First, the polyketone resin used in the present invention is an engineering plastic and recently developed as a new resin, it is excellent in mechanical properties such as impact strength and molding characteristics, and is excellent in thermoplastic properties It is synthetic resin. The mechanical properties of the polyketone resin belong to the category of high performance plastics, and they are attracting much attention as eco-friendly materials because they are polymeric materials synthesized from carbon monoxide as a raw material.

Polyketone resin has lower moisture absorption than polyamide material, so it is possible to design various products with less changes in dimensions and physical properties due to moisture absorption. Especially, polyketone resin is more suitable for weight reduction because it has lower density than aluminum material.

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

The production process of polyketone is carried out in the presence of an organometallic complex catalyst comprising (a) a Group 9, 10 or 11 transition metal compound, and (b) a ligand having an element of Group 15, A process for producing a polyketone by terephthalic copolymerization of an ethylenic and a propylenically unsaturated compound is characterized in that a mixed solvent of 70 to 90% by volume of acetic acid and 10 to 30% by volume of water is used as a liquid medium and benzophenone .

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

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

Wherein the catalyst comprises (a) a Group 9, 10 or 11 transition metal compound of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature, 1989) and (b) a ligand having an element of Group 15 elements.

Examples of the Group 9 transition metal compound in the ninth, tenth, or eleventh group transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamates, and sulfonates, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate, and ruthenium trifluoromethanesulfonate.

Examples of the Group 10 transition metal compounds include complexes of nickel or palladium, carbonates, phosphates, carbamates, sulfonates and the like. Specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, palladium trifluoroacetate , Palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium and palladium sulfate.

Examples of the Group 11 transition metal compound include copper or silver complexes, carbonates, phosphates, carbamates, and sulfonates, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, Examples of the fluoroacetic acid include silver acetyl acetate, trifluoromethanesulfonic acid and the like.

Of these, the transition metal compound (a), which is preferable inexpensively and economically, is nickel and copper compounds, and the preferable transition metal compound (a) in terms of the yield of the polyketone and the molecular weight is the palladium compound, It is most preferable to use palladium acetate.

Examples of the ligands (b) having an atom of Group XIII include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'- Bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) (2-methoxyphenyl) propane, 1,3-bis [di (2-isopropyl) Bis (diphenylphosphino) cyclohexane, 1,2-bis (diphenylphosphino) phosphine] propane, (Diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) (Diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxy- (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2- Spinosyns; there may be mentioned a ligand, such as propane.

Among these ligands, preferred ligands (b) having a Group 15 element are phosphorus ligands having an atom of Group 15, and particularly preferred ligands in terms of yield of polyketone are 1,3-bis [di (2- Methoxyphenyl) phosphino] propane and 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, Di (2-methoxyphenyl) phosphino] propane, and it is safe in that it does not require an organic solvent. Soluble sodium salts such as 1,3-bis [di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino] propane, 1,2- ] Methyl] benzene, and 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane are preferred for ease of synthesis and availability in large quantities and economically. The preferred ligand (b) having a Group 15 atom is 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis (diphenylphosphino) Bis (di (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5- -Methoxyphenyl) phosphine).

[Chemical Formula 1]

Figure 112017059265403-pat00001
.

Bis (bis (2-methoxyphenyl) phosphine) bis ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Activity equivalent to that of 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, which is known to exhibit the highest activity among polymerization catalysts The structure is simpler and has a lower molecular weight. As a result, the present invention has been able to provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst of the present invention, while further reducing its manufacturing cost and cost. A method for producing a ligand for a polyketone polymerization catalyst is as follows. ((2,2-dimethyl) -2,3-dioxolane was obtained by using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) is obtained by reacting a bis (methylene) . The process for preparing a ligand for a polyketone polymerization catalyst according to the present invention is a process for producing a ligand for a polyketone polymerization catalyst which comprises reacting 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially synthesized in a large amount.

It is also preferable to use bis (bis (2-methoxyphenyl) phosphine as the ligand (cyclohexane-1,1-diylbis (methylene)) bis Respectively.

Figure 112017059265403-pat00002

In a preferred embodiment, the process for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises: (a) introducing bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) into a reaction vessel under nitrogen atmosphere, Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the resulting mixture, followed by stirring and reacting; (c) adding methanol and stirring after completion of the reaction; (d) adding toluene and water, separating the layers, washing the oil layer with water, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue was recrystallized from methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5- diyl) bis (methylene)) bis (bis (2- methoxyphenyl) And then performing a step of acquiring

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

Further, the addition of benzophenone in the polymerization of the polyketone is another characteristic. In the present invention, an effect of improving the intrinsic viscosity of the polyketone can be achieved by adding benzophenone in the polymerization of the polyketone. The molar ratio of (a) the ninth, tenth, or eleventh transition metal compound to benzophenone is 1: 5-100, preferably 1:40-60. If the molar ratio of the transition metal to the benzophenone is less than 1: 5, the effect of improving the intrinsic viscosity of the produced polyketone is unsatisfactory. If the molar ratio of the transition metal to the benzophenone exceeds 1: 100, It is not preferable because it tends to decrease

Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, -Olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclo undecene, pentacyclopentadecene, pentacyclohexadecene, Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Ethyl acrylate, and acrylates such as methyl acrylate. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, most preferably ethylene, and 120 mol% propylene is added in the production of the terpolymerized polyketone.

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

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

Wherein the carbon monoxide and the ethylenically unsaturated compound and the propylenically unsaturated compound are copolymerized with an organometallic complex comprising a ligand (b) having an element of group 9, group 10 or group 11 transition metal compound (a) or group 15 Catalyzed, the catalyst is produced by contacting the two components. Any method may be employed as the method of contacting. That is, the solution may be prepared as a solution in which two components are premixed in a suitable solvent, or the two components may be supplied separately to the polymerization system and contacted in the polymerization system.

As the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, a vapor phase polymerization method in which a small amount of a polymer is impregnated with a high concentration catalyst solution, and the like are used. The polymerization may be either batchwise or continuous. The reactor used in the polymerization can be used as it is or in a known manner. The polymerization temperature is not particularly limited, and is generally 40 to 180 占 폚, preferably 50 to 120 占 폚. The pressure at the time of polymerization is not particularly limited, but is generally from normal pressure to 20 MPa, preferably from 4 to 15 MPa.

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

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

 When the polyketone terpolymer is used as the main polymer component of the blend of the present invention, there are at least two units containing an ethylene moiety in each unit containing the second hydrocarbon moiety in the terpolymer. It is preferable that the number of units containing the second hydrocarbon moiety is from 10 to 100.

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

(2)

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

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

In another embodiment, the polyketone polymer is a copolymer comprising repeating units represented by the general formulas (1) and (2), and y / x is preferably 0.03 to 0.3. When the value of the y / x value is less than 0.03, there is a limit in that the meltability and processability are inferior. When the value of y / x is more than 0.3, the mechanical properties are poor. Further, y / x is more preferably 0.03 to 0.1.

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

- [- CH2 --CH (CH3) - CO] y - (2)
(x and y represent mol% of each of the general formulas (1) and (2) in the polymer)

On the other hand, the polyketone resin preferably has an intrinsic viscosity (LVN) of 0.5 to 10 dl / g, more preferably 0.8 to 4 dl / g, and most preferably 1 to 1.5 dl / g. If the intrinsic viscosity of the polyketone resin is less than 0.5 dl / g, the mechanical properties may be deteriorated. If the intrinsic viscosity exceeds 10 dl / g, the workability may be deteriorated.

Particularly preferred are polyketone polymers having a number average molecular weight of from 100 to 200,000, especially from 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer are determined according to the molecular weight, depending on whether the polymer is a copolymer or a terpolymer and, in the case of a terpolymer, the properties of the second hydrocarbon part. The melting point of the total of the polymers used in the present invention is 175 ° C to 300 ° C, and generally 210 ° C to 270 ° C. The intrinsic viscosity (LVN) of the polymer measured by HFIP (hexafluoroisopropyl alcohol) at 60 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, preferably 0.8 dl / g to 4 dl / g, And more preferably 1.0 dl / g to 2.0 dl / g. If the intrinsic viscosity is less than 1.0 dl / g, the mechanical properties are deteriorated. If the intrinsic viscosity exceeds 2.0 dl / g, the workability is deteriorated.

On the other hand, the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. When the ratio is less than 1.5, the polymerization yield decreases. When the ratio is more than 2.5, the moldability is poor. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst is increased or when the polymerization temperature is 100 ° C or higher, the molecular weight distribution becomes larger.

Specifically, the polyketone composition improved in surface appearance of the present invention comprises a linear alternating polyketone composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon, a polyhydric alcohol and a glass fiber of C2 to C20 wherein the polyhydric alcohol is ethylene Glycol, glycerol, pentaerythritol, sorbitol, dipentaerythritol, and the like.

In this case, the ratio of the polyketone to the polyhydric alcohol is preferably 80 to 97 parts by weight: 3 to 20 parts by weight. When the polyketone is less than 80 parts by weight, there may be a problem of physical properties and appearance defects due to a problem of dispersion of polyketone and polyhydric alcohol. When the amount is more than 97 parts by weight, the surface improving effect is insufficient.

On the other hand, the content of the glass fiber is preferably 20 to 60% by weight based on the total weight of the polyketone composition. If the content of the glass fiber is less than 20% by weight, the effect of improving the physical properties such as strength improvement is insufficient. If the content is more than 60% by weight, the workability is deteriorated.

It is also preferable that the crystallization temperature (DSC) has a crystallization temperature of 150 to 175 ° C and a crystallinity of 10 to 35%. When the crystallization temperature and the crystallization degree are out of the upper limit value and the lower limit value, surface characteristics such as roughness and gloss are lowered, and workability is lowered and production is difficult.

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

The method for producing a polyketone composition of the present invention comprises: preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bidentate compound of phosphorus; Preparing a mixed solvent (polymerization solvent) containing an alcohol (for example, methanol) and water; Conducting the polymerization in the presence of the catalyst composition and the mixed solvent to prepare a linear terpolymer of carbon monoxide, ethylene and propylene; Removing the remaining catalyst composition from the linear terpolymer with a solvent (e.g., alcohol and acetone) to obtain a polyketone resin; And mixing the polyketone resin with a C2 to C20 polyhydric alcohol and glass fiber to prepare a composition, but the present invention is not limited thereto.

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

As the acid having a pKa value of 6 or less constituting the catalyst composition, at least one selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid and sulfonic acid, preferably trifluoroacetic acid, may be used. 6 to 20 (mol) equivalents relative to the compound is appropriate.

Examples of the bidentate ligand compound constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (e.g., 1,3-bis [di (2-methoxyphenylphosphino) propane) Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane, ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Methylene)) bis (bis (2-methoxyphenyl) phosphine) and (cyclohexane-1,1-diylbis (methylene)) bis Or more, and the amount thereof to be used is suitably 1 to 1.2 (molar) equivalent based on the palladium compound.

The carbon monoxide, ethylene and propylene are liquid phase polymerized in a mixed solvent of alcohol (e.g. methanol) and water to produce a linear terpolymer. As the mixed solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of water in the mixed solvent is less than 2 parts by weight, a ketal may be formed to lower the heat stability in the process. If the amount is more than 10 parts by weight, the mechanical properties of the product may be deteriorated.

The polymerization temperature is preferably in the range of 50 to 100 ° C and the reaction pressure in the range of 40 to 60 bar. The resulting polymer is recovered through filtration and purification processes after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

In the present invention, the obtained polyketone resin is mixed with a polyhydric alcohol of C2 to C20 and glass fiber, and then extruded by an extruder to finally obtain a polyketone composition. The blend may be prepared by charging it into a twin-screw extruder and melt-kneading and extruding it.

In this case, the extrusion temperature is preferably 230 to 260 ° C, and the screw rotation speed is preferably in the range of 100 to 300 rpm. If the extrusion temperature is less than 230 캜, kneading may not occur properly, and if the extrusion temperature exceeds 260 캜, problems related to the heat resistance of the resin may occur. If the screw rotation speed is less than 100 rpm, smooth kneading may not occur.

In addition, the polyketone composition may be injected to produce parts such as a faucet bracket, a railway rail part, and an automobile interior / exterior part using a polyketone composition having an improved surface appearance.

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

[Example 1]

Linear alternating polyketones comprised of carbon monoxide and ethylene and propene were prepared from palladium acetate, trifluoroacetic acid, and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) The content of trifluoroacetic acid relative to palladium is 10 times the molar ratio and is subjected to two steps of a first stage at a polymerization temperature of 78 DEG C and a second stage at 84 DEG C. In the polyketone terpolymer prepared above, And propene was 85 to 15. The melting point of the polyketone terpolymer was 220 DEG C and the LVN measured at 25 DEG C using HFIP (hexa-fluoroisopropano) was 1.4 dl / g, and the MWD was 2.0. The prepared terpolymer is named M930A.

A composition was prepared by blending 61.1% by weight of the polyketone terpolymer (M930), 3.9% by weight of pentaerythritol (PETOL) (M930: PETOL = 94: 6) and 35% by weight of glass fibers, A pellet was formed on the extruder using a twin-screw with a diameter of 40 cm, operating at 250 rpm and L / D = 32. On the other hand, the polyketone (M930) has a melt index (MI) of 45 g / 10 min.

[Example 2]

Except that 58.5% by weight of polyketone (M930), 6.5% by weight of pentaerythritol (PETOL) (M930: PETOL = 9: 1) and 35% by weight of glass fibers were used in Example 1.

[Example 3]

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

A composition was prepared by blending 58.5 wt% of the polyketone terpolymer (M330), 6.5 wt% of pentaerythritol (PETOL) (M330: PETOL = 9: 1) and 35 wt% of glass fiber, A pellet was formed on the extruder using a twin-screw with a diameter of 40 cm, operating at 250 rpm and L / D = 32. On the other hand, the polyketone (M330) has a melt index (MI) of 27 g / 10 min.

[Comparative Example 1]

 Except that 65 wt% of polyketone (M930) and 35 wt% of glass fiber were used in Example 1 above.

[Comparative Example 2]

 Except that 65 wt% of polyketone (M330) and 35 wt% of glass fiber were used in Example 3 above.

Property evaluation

The physical properties of the specimens prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated by the following methods. The results are shown in Table 1 below.

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

       2. Tensile strength: ASTM D638. Initial tensile strength and tensile strength were measured after aging for 72 hours in an oven maintained at 180 ° C.

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

4. Crystallization temperature: The temperature of the exothermic peak formed at a temperature of 130 to 200 ° C in the second falling temperature curve on the DSC was measured as the crystallization temperature. The rate of temperature rise and fall is 20 ° C / min. The upper limit of the temperature rise was 240 o C in consideration of the melting point of polyketone and the lower limit of temperature was -40 o C.

5. Crystallinity: The enthalpy of fusion of the endothermic peak formed in the temperature range of 150-240 ° C in the secondary temperature rise curve on the DSC is divided by the resin fraction, and then the crystallite size is 230 J / g. The heating / cooling conditions were the same as those described in the crystallization temperature measurement method.

Crystallinity = endothermic peak area / resin fraction / 230 x 100 (%)

Resin fraction = (1-additive weight ratio) x GF weight ratio

division Resin composition Melt Index
(g / 10 min)
Glass fiber
content
(wt%)
Crystallization behavior (DSC) Exterior Properties
crystallization
Temperature (℃)
Crystallinity
(%)
Flow
mark
Illuminance
(um)
Gloss
(GU)
Seal
burglar
(MPa)
Notched
Charpy
(kJ / m 2 )
compare
Example 1
M930 45 35 182 21 X ~ Δ 0.80 45 160 12.8
practice
Example 1
M930-PETOL
(94: 6)
45 35 171 23 O 0.29 54 156 11.0
practice
Example 2
M930-PETOL
(90:10)
45 35 160 18 Δ~O 0.24 54 154 10.1
compare
Example 2
M330 27 35 180 32 X 0.44 47 154 13.0
practice
Example 3
M330- PETOL
(90:10)
27 35 162 17 Δ~O 0.22 54 153 11.6

The determination criteria of O,?, And X of the flow mark in the outer part of the above table are shown in Fig.

       As shown in Table 1, it can be seen that the crystallization temperature and the degree of crystallization in Examples were lower than those of Comparative Examples.

On the other hand, the surface appearance was superior to that of the comparative example, and when the additive was added to the polyketone, the crystallization temperature and the degree of crystallization were lowered as compared with the comparative example containing only polyketone, It can be confirmed that it is improved.

The polyketone composition of the present invention having an improved surface appearance can be used for manufacturing an outer jacket of a water meter.

Claims (6)

  1. A polyketone copolymer comprising repeating units represented by the following chemical formulas (1) and (2), wherein 58.5 to 61.1% by weight of a linear alternating polyketone with y / x of 0.03 to 0.3;
    3.9 to 6.5 wt% of a C2 to C20 polyalcohol (multi hydroxyl (-OH) alcohol); And
    35% by weight of glass fibers;
    Wherein the crystallization temperature is 160 to 171 DEG C and the crystallinity is 17 to 23%.
    - [- CH2CH2-CO] x- (1)
    - [- CH2 --CH (CH3) - CO] y - (2)
    (x and y represent mol% of each of the general formulas (1) and (2) in the polymer)
  2. The method according to claim 1,
    Wherein the polyhydric alcohol is at least one selected from the group consisting of ethylene glycol, glycerol, pentaerythritol, sorbitol and dipentaerythritol, and the polyhydric alcohol is at least one selected from the group consisting of ethylene glycol, glycerol, pentaerythritol, sorbitol and dipentaerythritol A polyketone composition having improved surface appearance.
  3. delete
  4. delete
  5. delete
  6. A water meter outer cover manufactured by using the polyketone composition according to claim 1 or 2.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100445354B1 (en) 1998-08-10 2004-08-21 아사히 가세이 가부시키가이샤 Polyketone solution
KR101706050B1 (en) 2014-11-19 2017-02-14 주식회사 효성 Polyketone composition comprising glass fiber

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6001955A (en) * 1998-09-15 1999-12-14 Shell Oil Company High modulus polyketones
KR101684896B1 (en) * 2014-11-19 2016-12-12 주식회사 효성 Polyketone vehicle valve body

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100445354B1 (en) 1998-08-10 2004-08-21 아사히 가세이 가부시키가이샤 Polyketone solution
KR101706050B1 (en) 2014-11-19 2017-02-14 주식회사 효성 Polyketone composition comprising glass fiber

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