KR20200001391A - Polyketone Composition Containing Plasticizer - Google Patents

Abstract

The present invention provides a polyketone composition comprising 50 to 99 wt% of polyketone, and 1 to 50 wt% of at least one plasticizer selected from chemical formula 1a and chemical formula 1b, based on a total weight of a composition. The polyketone composition according to the present invention is capable of injection molding, extrusion molding, blowing molding and the like.

Description

Polyketone composition containing plasticizer {Polyketone Composition Containing Plasticizer}

The present invention relates to polyketone compositions comprising polyketones and certain plasticizers.

Recently, there has been a growing interest in polyketones having a structure in which a polymer of carbon monoxide and at least one ethylenically unsaturated monomer, in particular a repeating unit derived from carbon monoxide and a repeating unit derived from an ethylenically unsaturated monomer, is alternately connected. This is because the polyketone has excellent mechanical and thermal properties, high abrasion resistance, chemical resistance and gas barrier properties, and is a useful material for various applications.

The high molecular weight polymer of polyketone has higher mechanical and thermal properties and is considered to be useful as an economical engineering plastic material. In particular, the wear resistance is high, and parts such as automobile gears and chemical resistance are high, so that the gas barrier properties, such as lining material of chemical transport pipes and various chemical bottles, are high, and can be used for light gasoline tanks. In addition, when the ultra high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for the fibers, the fibers can be stretched at a high magnification, and have a high strength and a high modulus of elasticity oriented in the stretching direction. It is very suitable for building materials and industrial materials.

Such polyketones are usually compounds of group VIII metals selected from palladium, cobalt and nickel, anions of non-hydrohalogentic acids, phosphorus, arsenic or antimones. It can be prepared using a catalyst composition generated from the bidentate ligand of.

U.S. Pat. Nos. 4,880,903 and 5,369,170 disclose polyketones, copolymers of carbon monoxide, ethylene and other olefinically unsaturated monomers, and U.S. Pat. And a process for preparing a polymer of carbon monoxide and at least one ethylenically unsaturated monomer using a catalyst consisting of a bidentate ligand of phosphorus, the disclosures of which are incorporated herein by reference.

However, polyketone has a melting point higher than the molding temperature range of conventional molding methods such as injection molding, extrusion molding, blow molding, etc., and is difficult to use due to the deterioration of flowability and fluidity during extrusion and injection processing, and in the form of a film. Not only is difficult to process, but also has problems such as color change and brittleness of the molded article.

In this regard, some prior arts suggest blends with other polymers, etc., but certain limitations exist.

Accordingly, an object of the present invention is to solve the problems of the prior art as described above and the technical problems that have been requested from the past.

The inventors of the present application, through in-depth studies and various experiments, have developed a composition including a specific plasticizer in a polyketone, and the polyketone composition has a melting point below a general molding temperature range without deteriorating the physical properties of the polyketone itself. It can be lowered, it was confirmed that the heat stability in the molding process is excellent and can minimize the generation of fume and completed the present invention.

Polyketone composition according to the present invention for achieving this object,

50% to 99% by weight of polyketone, and at least one plasticizer selected from the following Formulas 1a and 1b, characterized in that it comprises 1 to 50% by weight based on the total weight of the composition.

(1a)

(1a)

(1b)

(1b)

Where

R ₁ and R ₃ are each independently OH, OCH ₃ , OCH ₂ OH, O (CH ₂ ) _n CH ₃ , O (CH ₂ ) _n CH ₂ OH, OC ₆ H ₅ , OC ₆ H ₄ OH, O ( CH ₂ ) _n C ₆ H ₅ , O (CH ₂ ) _n C ₆ H ₄ OH, O (CH ₂ ) _n C ₆ H ₄ CH ₂ OH, OC ₆ H ₁₁ , OC ₆ H ₁₀ OH, OC ₆ H ₁₀ CH ₂ OH, O (CH ₂ ) _n C ₆ H ₁₁ , O (CH ₂ ) _n C ₆ H ₁₀ OH or O (CH ₂ ) _n C ₆ H ₁₀ CH ₂ OH, where n is from 1 to 20 Natural water, preferably 1 to 10 natural water;

R ₂ is (CH ₂ ) _m , [(CH ₂ ) _m -C ₆ H ₄ ] _p , [(CH ₂ ) _m -C ₆ H ₁₀ ] _q , [(CH ₂ ) _a -X- (CH ₂ ) _b ] _s , [(CH ₂ ) _a -X- (CH ₂ ) _b -Y- (CH ₂ ) _c ] _t or [(CH ₂ ) _a C (CH ₃ ) ₂ (CH ₂ ) _{a '} -X- (CH ₂ ) _b C (CH ₃ ) ₂ (CH ₂ ) _{b '} ] _s ;

here,

m is a natural number of 1 to 20, preferably a natural number of 1 to 10;

X and Y are independently of each other C ₆ H ₄ , C ₆ H ₁₀ , O, CO ₂ , OCO ₂ , O ₂ C Or NH;

a, a ', b, b' and c are each independently a natural number of 1 to 20, preferably 1 to 10 natural numbers;

p, q, s and t are each independently a natural number of 1 to 5,

R ₄ and R ₆ independently of one another are H, CH ₃ , CH ₂ OH, (CH ₂ ) _n CH ₃ , (CH ₂ ) _n CH ₂ OH, C ₆ H ₅ , C ₆ H ₄ OH, (CH ₂ ) _n C ₆ H ₅ , (CH ₂ ) _n C ₆ H ₄ OH, (CH ₂ ) _n C ₆ H ₄ CH ₂ OH, C ₆ H ₁₁ , C ₆ H ₁₀ OH, C ₆ H ₁₀ CH ₂ OH, ( CH ₂ ) _n C ₆ H ₁₁ , (CH ₂ ) _n C ₆ H ₁₀ OH, (CH ₂ ) _n C ₆ H ₁₀ CH ₂ OH, (CH ₂ ) _n OCO ₂ (CH ₂ ) _{n '} H or (CH _{2) n OCO 2 (CH 2} ) n ' OH, and, wherein, n and n' is a natural number between 1 and 20, preferably between 1 and 10, a natural number;

R ₅ is (CH ₂ ) _m , where m is a natural number of 1 to 20, preferably a natural number of 1 to 10,

CH ₂ , (CH ₂ ) _n , (CH ₂ ) _m , C ₆ H ₅ , C ₆ H ₄ , C ₆ H ₁₁ And C ₆ H _{10 −} are a substituted or unsubstituted structure, and in the case of a substituted structure, at least one hydrogen is substituted with a C ₁ -C ₅ alkyl group.

In one specific example, the C ₁ -C ₅ alkyl group may be a methyl group, ethyl group, propyl group, 2-methyl propyl group, butyl group, 2-methyl butyl group, or tert-butyl group, preferably methyl group Can be.

In the polyketone composition of the present invention, the polyketone, as described above, contains substantially one molecule of carbon monoxide for each molecule of the ethylenically unsaturated monomer. The moiety derived from CO alternates with the moiety derived from ethylenically unsaturated monomers.

The ethylenically unsaturated monomer may have 20, more specifically up to 10 carbon atoms. For example, aliphatic monomers such as ethane, propene, 1-butene, isobutene, 1-hexene, 1-octene Or an aryl aliphatic monomer comprising an aryl substituent on another aliphatic molecule, in particular an aryl substituent on an ethylenically unsaturated carbon atom. Monomers of aryl aliphatic hydrocarbons among the ethylenically unsaturated monomers include styrene, p-methyl styrene, p-ethyl styrene, and m-isopropyl styrene. Can be mentioned.

Although it is possible to use a plurality of different ethylenically unsaturated monomers in the same polymer, in one specific example, the polyketone is represented by the following formula (2) and comprises a homogenous unsaturated monomer having carbon monoxide and at least two carbon atoms Homopolymers or linear alternating copolymers comprising an α-olefin such as carbon monoxide, ethylene and an ethylenically unsaturated monomer having at least three carbon atoms, in particular propylene.

(2)

(2)

(3)

(3)

Where

A is an aliphatic hydrocarbon derived from an ethylenically unsaturated monomer having at least two carbon atoms;

u is 2 to 100;

v is 10 to 100, w is 1 to 50, and the ratio of v / w is 2 to 100.

When the polyketone of formula 3 is used as the main component of the polyketone composition of the present invention, there are about 10 to 100 units containing aliphatic hydrocarbons derived from ethylenically unsaturated monomers having at least 3 carbon atoms. And there are at least two units in the copolymer comprising aliphatic hydrocarbons derived from ethylene for each unit containing such aliphatic hydrocarbons. In addition, units comprising aliphatic hydrocarbons derived from ethylene and units comprising aliphatic hydrocarbons are found randomly throughout the polymer chain.

Additional monomers may also be used and still fall within the scope of the polyketones described herein. That is, polyketones may be made from a combination of four, five, or more monomers.

Particular preference is given to polyketones having a number average molecular weight of about 1000 to about 200,000 as measured by gel permeation chromatography, in particular polyketones having a number average molecular weight of about 20,000 to about 90,000. The physical properties of the polymer will depend on the molecular weight regardless of whether the polymer is a homopolymer or a copolymer, and in the case of the copolymer will also depend in part on the proportion or properties of the aliphatic hydrocarbons present.

As described above, the method for preparing the polyketone is known from US Pat. No. 4,843,144, so a detailed description thereof is omitted herein.

As described above, polyketone is generally excellent in physicochemical properties such as chemical resistance, heat resistance and impact resistance, but in the case of heat resistance, it is difficult to be extruded and injected due to gelation when it is left for a long time at 240 degrees Celsius or longer at 260 degrees Celsius. Is holding. In addition, since the fluidity is not secured during extrusion and injection, when the film is manufactured through blow molding after extrusion, the film may be thickly formed, so that it is difficult to control the thickness and is difficult to manufacture the film due to brittle problems. Have.

On the other hand, the polyketone composition according to the present invention, as can be confirmed in the experimental results described later, by lowering the melting point within the general molding temperature range to ensure fluidity, injection molding, extrusion molding, blowing molding, etc. In addition, the molded article accordingly does not have problems such as color change or brittleness. In particular, the polyketone composition according to the present invention can be excellent in heat resistance stability in the molding conditions and the generation of fumes (fume) can be minimized.

The plasticizer used in the polyketone composition according to the present invention provides such properties and does not elute after molding without affecting the intrinsic physical properties of the polyketone.

In Formula 1a, R ₁ and R ₃ may be, in one preferred example, independently of each other, OCH ₃ or O (CH ₂ ) _n CH ₃ (a natural number of n = 1 to 5), and more preferably, OCH ₃ , OCH ₂ CH ₃ , OCH ₂ CH ₂ CH ₃ , or OCH ₂ CH ₂ CH ₂ CH ₃ .

R ₂ is, in one preferred example, (CH ₂ ) _m , [(CH ₂ ) _a -X- (CH ₂ ) _b ] _s or [(CH ₂ ) _a -X- (CH ₂ ) _b -Y- (CH ₂ ) _c ] _t , more preferably [(CH ₂ ) _a -X- (CH ₂ ) _b ] _s or [(CH ₂ ) _a -X- (CH ₂ ) _b -Y- ( CH ₂ ) _c ] _t . Here, preferably X and Y may be independently of each other O, CO ₂ , OCO ₂ or O ₂ C.

In another preferred example, the molecular weight of the R ₂ moiety may be between 100 and 3,000, more preferably between 500 and 2,000.

In Formula 1b, R ₄ and R ₆ , in one preferred embodiment, independently of one another, (CH ₂ ) _n CH ₂ OH, (CH ₂ ) _n OCO ₂ (CH ₂ ) _{n ′} H or (CH ₂ ) _n OCO ₂ (CH _{2) n} may be a _'and OH, where, n and n' is a natural number of 1 to 5.

In the polyketone composition of the present invention, the content of the plasticizer is 1% by weight to 50% by weight based on the total weight of the composition as defined above, and when the content of the plasticizer is too low, it may be difficult to achieve the purpose of lowering the melting point, On the contrary, too much of the plasticizer is not preferable because of excessively high fluidity, which may be difficult to mold and may cause a decrease in physical properties of the molded article.

The content of the plasticizer may preferably be 3 to 35% by weight, more preferably 5 to 30% by weight, particularly preferably 10 to 25% by weight.

In some cases, the plasticizer of Chemical Formula 4 may be further included in addition to the plasticizer of Chemical Formulas 1a and / or 1b in a range in which the total amount of the plasticizer does not deviate from the above range.

(4)

(4)

Where

R ₇ is OH, OCH ₃ , O (CH ₂ ) _n CH ₃ , OC ₆ H ₅ , O (CH ₂ ) _n C ₆ H ₅ , OC ₆ H ₁₁ or O (CH ₂ ) _n C ₆ H ₁₁ , Where n is a natural number from 1 to 20;

R ₈ is CH ₃ , OH, CO ₂ H, OCH ₃ , O (CH ₂ ) _n CH ₃ , OC ₆ H ₅ , O (CH ₂ ) _n C ₆ H ₅ , OC ₆ H ₁₁ , O (CH ₂ ) _n C ₆ H ₁₁ , CO ₂ CH ₃ , CO ₂ (CH ₂ ) _n CH ₃ , CO ₂ C ₆ H ₅ , CO ₂ (CH ₂ ) _n C ₆ H ₅ , CO ₂ C ₆ H ₁₁ or CO ₂ ( CH ₂ ) _n C ₆ H ₁₁ , wherein n is a natural number from 1 to 20;

k is a natural number from 1 to 20.

The content of the Chemical Formula 4 plasticizer may be, for example, 5 to 95 parts by weight based on 100 parts by weight of the formula 1a and / or 1b plasticizer.

In one preferred example, R ₇ is OCH ₃ , OCH ₂ CH ₃ or OC ₆ H ₁₁ , R ₈ is CH ₃ , OH or CO ₂ H and k may be a natural number from 1 to 8.

The polyketone composition of the present invention may further include other known polymers, and these other polymers are well known in the art, and thus detailed description thereof will be omitted.

The present invention also provides a molding obtained by molding the polyketone composition.

Examples of the molding include injection molding, extrusion molding, blowing molding, and the like, but are not limited thereto.

As described above, in the polyketone composition according to the present invention, the melting point is lowered within the general molding temperature range, and thus injection molding, extrusion molding, blowing molding, and the like are possible, and thus the molded article also has problems such as color change or brittleness. It does not have, it is excellent in heat resistance stability during the molding process has the advantage of minimizing the generation of fumes.

1 is a FT-IR analysis graph of the synthetic material of Example 1;
2 is a FT-IR analysis graph of the synthetic material of Example 3;
3 is a FT-IR analysis graph of the synthetic material of Example 7;
4 is a FT-IR analysis graph of the synthetic material of Example 11;
5 is a FT-IR analysis graph for the synthetic material of Example 14;
6 is a DSC analysis graph of the polyketone composition of Comparative Example 1;
7 is a DSC analysis graph for the polyketone composition of Example 7;
8 is a DSC analysis graph for the polyketone composition of Example 11;
9 is a DSC analysis graph for the polyketone composition of Example 15.

Hereinafter, although described in more detail with reference to some embodiments according to the present invention, of course, the scope of the present invention is not limited thereto.

Example 1

To 500 g (5.4 mol) of toluene, 176 g (2 mol) of 1,3-dioxolan-2-one, 5 g (0.03 mol) of cesium hydroxide (CsOH) as a catalyst, and 50 ml of water were added. In a reactor equipped with a stirrer and a mantle, the reaction was carried out at a temperature of 80 degrees for 12 hours to form one functional group in the form of alcohol. The added water was removed by distillation at elevated temperature, and the reaction was completed at 150 ° C for 12 hours to complete the reaction, and then neutralized with 500 ml of 5% dilute hydrochloric acid aqueous solution and extracted with methylene dichloride solvent. Then, the solvent was distilled under reduced pressure to synthesize ethylene glycol dicarboxylic acid, and it was confirmed that carboxylic acid having the following chemical formula was produced using FT-IR.

Referring to FIG. 1, the OH strech peak of the carboxylic acid appears at 2900 cm ⁻¹ , the C═O strech peak appears at 1700 cm ⁻¹ , and the CO strech peak appears at 1250 cm ⁻¹ . Thus, it can be confirmed that ethylene glycol dicarboxylic acid was synthesized.

A polyketone composition was prepared by mixing 5% by weight of the compound as a plasticizer and 95% by weight of polyketone (Hyosung Co., Ltd .; M 710).

Example 2

To 500 g (5.4 mol) of toluene, add 204 g (2 mol) of 1,3-dioxan-2-one, 5 g (0.03 mol) of cesium hydroxide (CsOH) as a catalyst, and 50 ml of water. In a reactor equipped with a stirrer and a mantle, the reaction was carried out at a temperature of 80 degrees for 12 hours to form one functional group in the form of alcohol. The added water was removed by distillation at elevated temperature, and the reaction was completed at 150 ° C for 12 hours to complete the reaction, neutralized with 500 ml of 10% formic acid aqueous solution, and extracted with a methylene dichloride solvent. Then, the solvent was distilled under reduced pressure to synthesize dicarboxylic ester, and it was confirmed that carboxylic acid having the following chemical formula was produced using FT-IR.

A polyketone composition was prepared by mixing 5% by weight of the compound and 95% by weight of polyketone (M 710) as a plasticizer.

Example 3

500 g (15.6 mol) of methanol and 176 g (2 mol) of 1,3-dioxolan-2-one and 2 g (0.05 mol) of magnesium oxide (MgO) as a catalyst are placed in a four-necked flask equipped with a stirrer and a cooler. After refluxing for 6 hours at 90 degrees, methanol was distilled off to obtain 2-hydroxyethyl methylcarbonate. In this state, 1 g (0.017 mol) of magnesium hydroxide and 225 g (2.5 mol) of dimethyl carbonate were slowly added dropwise as a catalyst, followed by reflux at about 100 ° C. for 10 hours to complete the reaction, followed by 5% dilute hydrochloric acid. Neutralized and extracted with 500 ml of methylene chloride. Then, distillation under reduced pressure to synthesize a dicarbonate ester compound, using FT-IR to identify a carbonate compound of the following formula.

Referring to FIG. 2, the OH strech peak does not appear, the CH strech peak appears at 2960 cm ⁻¹ , the C═O strech peak appears at 1740 cm ⁻¹ , and the CO strech peak appears strongly at 1250 cm ⁻¹ . Thus, it can be confirmed that the dicarbonate ester compound was synthesized.

A polyketone composition was prepared by mixing 5% by weight of the compound and 95% by weight of polyketone (M 710) as a plasticizer.

Example 4

500 g (15.6 mol) of methanol and 204 g (2 mol) of 1,3-dioxan-2-one and 2 g (0.05 mol) of magnesium oxide (MgO) as a catalyst are placed in a four-necked flask equipped with a stirrer and a cooler. After refluxing for 6 hours at 90 degrees, methanol was distilled off to obtain 2-hydroxyethyl methylcarbonate. In this state, 1 g (0.017 mol) of magnesium hydroxide and 225 g (2.5 mol) of dimethyl carbonate were slowly added dropwise as a catalyst and refluxed at about 100 ° C. for 10 hours to complete the reaction, followed by dilute hydrochloric acid at 5%. Neutralize and extract with 500 ml of methylene chloride. Thereafter, the dicarbonate ester compound was synthesized by distillation under reduced pressure, and FT-IR was used to identify a carbonate compound represented by the following formula.

A polyketone composition was prepared by mixing 5% by weight of the compound and 95% by weight of polyketone (M 710) as a plasticizer.

Example 5

500 g (15.6 mol) of methanol and 204 g (2 mol) of 4-methyl-1,3-dioxolan-2-one and 2 g (0.05 mol) of magnesium oxide (MgO) as a catalyst are equipped with a stirrer and a cooler. The mixture was refluxed at 90 ° C. for 6 hours, and methanol was distilled off to obtain 1-methyl-2-hydroxyethyl-methylcarbonate. In this state, 1 g (0.017 mol) of magnesium hydroxide and 225 g (2.5 mol) of dimethyl carbonate were slowly added dropwise as a catalyst, and the mixture was refluxed at about 100 ° C for 10 hours to complete the reaction, followed by 5% dilute hydrochloric acid. Neutralize and extract with 500 ml of methylene chloride. Thereafter, the dicarbonate ester compound was synthesized by distillation under reduced pressure, and FT-IR was used to identify a carbonate compound represented by the following formula.

A polyketone composition was prepared by mixing 5% by weight of the compound and 95% by weight of polyketone (M 710) as a plasticizer.

Example 6

719 g (15.6 mol) of ethanol, 204 g (2 mol) of 1,3-dioxan-2-one and 2 g (0.05 mol) of magnesium oxide (MgO) as a catalyst are placed in a four-necked flask equipped with a stirrer and a cooler. After refluxing at 100 ° C. for 10 hours, ethanol was distilled off to obtain 3-hydroxypropyl-ethylcarbonate. In this state, 1 g (0.017 mol) of magnesium hydroxide and 295 g (2.5 mol) of diethyl carbonate were slowly added dropwise as a catalyst, followed by reflux at about 140 ° C. for 12 hours to complete the reaction, followed by 5% dilute hydrochloric acid. Neutralized and extracted with 800 ml of methylene chloride. Thereafter, the dicarbonate ester compound was synthesized by distillation under reduced pressure, and FT-IR was used to identify a carbonate compound represented by the following formula.

A polyketone composition was prepared by mixing 5% by weight of the compound and 95% by weight of polyketone (M 710) as a plasticizer.

Example 7

410 g (2.5 mol) of trimethylene carbonate obtained in Example 2, 300 g (3 mol) of cyclohexanol, 2.5 g (0.0088 mol) of titanium isopropoxide and 250 g of xylene as a catalyst were prepared using a thermometer and water generated. After the reaction was performed at 230 degrees for 8 hours using a flask equipped with a removal device, unreacted cyclohexanol and xylene were removed under reduced pressure. Then, neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), filtered after washing with water and dehydrating. Cyclohexyl trimethylene carbonate of the formula

Referring to FIG. 3, the OH strech peak does not appear, the CH strech peak of the cyclohexyl group appears at 2900 cm ⁻¹ , the C═O strech peak appears at 1740 cm ⁻¹ , and the CO strech peak is strongly at 1250 cm ⁻¹ . appear. Thus, it can be confirmed that cyclohexyl trimethylene carbonate is obtained.

A polyketone composition was prepared by mixing 5% by weight of the compound and 95% by weight of polyketone (M 710) as a plasticizer.

Example 8

In the same manner as in Example 7, 410 g (2.5 mol) of trimethylene carbonate obtained in Example 2, 343 g (3 mol) of cyclohexylmethanol and 2.5 g (0.0088 mol) of tetraisopropyl titanate as a catalyst and xyl 250 g of lene was reacted at 230 ° C. for 8 hours using a flask equipped with a thermometer and a generator for removing water, and unreacted cyclohexyl methanol and xylene were removed under reduced pressure. Then, neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), washed with water, dehydrated and filtered. Methylcyclohexyl trimethylene carbonate of the following formula was obtained.

A polyketone composition was prepared by mixing 5% by weight of the compound and 95% by weight of polyketone (M 710) as a plasticizer.

Example 9

260 g (2.5 mol) of neopentyl glycol and 104 g (1 mol) of malonic acid were used as a catalyst and 1 g (0.01 mol) of phosphoric acid as a catalyst was used for 10 hours at 230 degrees Celsius using a flask equipped with a thermometer and a water removing device. After the reaction was proceeded to cool to room temperature. Then, neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), washed with water and dehydrated, and then depressurized to remove unreacted neopentylglycol which was not dissolved in water. Got.

A polyketone composition was prepared by mixing 5% by weight of the compound and 95% by weight of polyketone (M 710) as a plasticizer.

Example 10

414 g (1.5 mol) of dyneopentyl malonate obtained in Example 9 and 319 g (4.2 mol) of methylhydrogencarbonate were attached with a thermometer and generating water removing device as phosphoric acid 1 g (0.01 mol) as a catalyst. After the reaction was performed at 150 ° C. for 12 hours, the flask was cooled to room temperature. Neutralize with 5% sodium carbonate (Na ₂ CO ₃ ), wash and dehydrate, and remove the unreacted neopentylglycol which is not dissolved in water by depressurizing to obtain the dinepentyl maleic dicarbonate-based ester compound Got it.

A polyketone composition was prepared by mixing 5% by weight of the compound and 95% by weight of polyketone (M 710) as a plasticizer.

Example 11

207 g (1.5 mol) of phenoxyethanol and 152 g (2 mol) of methylhydrogencarbonate were charged at 150 degrees using a flask equipped with a thermometer and generating water removal device as a catalyst. After the reaction proceeded for 12 hours at cooled to room temperature. Then, neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), washed with water, dehydrated, and decompressed to remove unreacted methylhydrogencarbonate in water. Nate ester compound was obtained.

Referring to FIG. 4, a CH stretch (aromatic) peak appears at 3050 cm ⁻¹ , a C═O strech peak appears at 1750 cm ⁻¹ , and a CO strech peak appears strongly at 1150 cm ⁻¹ . Thus, it can be confirmed that phenoxyethyl carbonate was synthesized.

A polyketone composition was prepared by mixing 4% by weight of the compound as a plasticizer, 1% by weight of the compound of Example 1, and 95% by weight of polyketone (M 710).

Example 12

207 g (1.5 mol) of phenylhydrogencarbonate and 180 g (2 mol) of butanediol were used as catalysts, and 0.5 g (0.005 mol) of phosphoric acid was used at a temperature of 220 degrees using a flask equipped with a thermometer and a dewatering device. After the reaction proceeded to cool to room temperature. Then, neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), washed with water, dehydrated, and distilled under reduced pressure to obtain 1-hydroxybutyl-phenylcarbonate, followed by 1-hydroxybutyl-phenylcarbonate 210 g (1 mol) and 0.5 g (0.005 mol) of phosphoric acid as catalysts in 114 g (1.5 mol) of methylhydrogencarbonate were used at a temperature of 150 degrees for 12 hours using a flask equipped with a thermometer and a water removal device. After the reaction was proceeded to cool to room temperature. Then, neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), washed with water, dehydrated, and then decompressed to remove unreacted methylhydrocarbonate carbonate, which was not dissolved in water, to give butylphenylcarbonate ester of the formula System compound was obtained.

A polyketone composition was prepared by mixing 4% by weight of the compound as a plasticizer, 1% by weight of the compound of Example 1, and 95% by weight of polyketone (M 710).

Example 13

450 g (3 mol) of ethylene glycol dicarboxylic acid and 298 g (4.8 mol) of ethylene glycol obtained in Example 1 were added, and 1 g (0.01 mol) of phosphoric acid was used in a flask equipped with a thermometer and a water removing device. After the reaction was carried out for 12 hours at 220 ° C it was cooled to room temperature. Then, neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), washed with water and dehydrated, and distilled under reduced pressure to synthesize ethylene glycol dicarboxylic ester ethylenedialcohol of the following formula.

A polyketone composition was prepared by mixing 5% by weight of the compound and 95% by weight of polyketone (M 710) as a plasticizer.

Example 14

590 g (1 mol) of ethylene glycol dicarboxylic ethylene dialcohol obtained in Example 13 and 182 g (2.4 mol) of methylhydrogencarbonate were generated as a catalyst and 0.5 g (0.005 mol) of phosphoric acid as a catalyst. The flask was equipped with a water removing apparatus and then reacted at 150 ° C. for 12 hours, and then cooled to room temperature. Then, neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), washed with water, dehydrated, and then decompressed to remove unreacted methylhydrogencarbonate not dissolved in water. A diethyl carbonate compound was obtained.

Referring to FIG. 5, the OH strech peak does not appear, the CH strech peak appears at 2850 cm ⁻¹ and 2950 cm ⁻¹ , the C═O strech peak appears at 1740 cm ⁻¹ , and the CO strech peak is 1250 cm ⁻¹ And 1120 cm ⁻¹ . Thus, it can be confirmed that ethylene glycol dicarboxylic ester diethyl carbonate is synthesized.

A polyketone composition was prepared by mixing 5% by weight of the compound and 95% by weight of polyketone (M 710) as a plasticizer.

Example 15

A polyketone composition was prepared by mixing 10 wt% of phenoxyethyl carbonate obtained in Example 11 and 90 wt% of polyketone (M 710) as a plasticizer.

Comparative Example 1

A polyketone composition was prepared in the same manner as in Example 1 except that no plasticizer was added.

Experimental Example 1

The polyketone compositions prepared in Examples 1 to 15 and Comparative Example 1 were melted and extruded in a twin screw extruder to prepare pellets, and then the flow characteristics (Melt Flow Index: MI) were measured. Provided in 1. MI was measured using the Model WL 1400 of Weed Lab Co., Ltd., and the reduction rate (%) was quantitatively displayed as the amount flowed down during the initial 1 minute under the condition of 4 minutes at 230 degrees Celsius. The measurement is a result of visually observing the color of each pellet by quantifying and displaying the amount of flowed down for 1 minute after finely cutting the pellet obtained in the first measurement.

TABLE 1

As shown in Table 1, compared with Comparative Example 1, it can be seen that the pellets prepared using the polyketone composition of the embodiments of the present invention have high fluidity and no color change. Therefore, it has been experimentally confirmed that it is useful for extrusion and injection molding.

Experimental Example 2

Differential thermal scanning calorimetry (DSC) thermal analysis was performed on the polyketone compositions prepared in Example 7, Example 11, Example 15 and Comparative Example 1 under the following experimental conditions.

Instrument: DSC Q20 V24.11 Build 124

Size: 2 mg or 2.4 mg

Exotherm: Up

Comment: 50 to 240, 10 / min, N2

The results are provided in Table 2 below and FIGS. 6 to 9.

TABLE 2

As shown in Table 2, the polyketone compositions of Examples 7, 11 and 15 can be seen that the melting point is significantly lowered. On the other hand, in Comparative Example 1, it can be seen that the primary melting point is high when the plasticizer is not added.

First, comparing the graph of Figure 7 showing the DSC results of the polyketone composition of Example 7 and Figure 6 showing the DSC results of Comparative Example 1, when the cyclohexyl trimethylene carbonate is mixed at 5% by weight primary The melting point at the time of heating is 192.24 degrees Celsius and the melting point at the time of secondary heating is 192.58 degrees Celsius, whereas in Comparative Example 1, which is 100% by weight of polyketone, the melting point at the time of first heating is 197.08 degrees Celsius, and the melting point at the time of secondary heating. You can see that it is 194.08 degrees Celsius. That is, the difference is about 4.84 degrees in the first heating and 1.5 degrees in the second heating.

Comparing FIG. 6 of Comparative Example 1 and FIG. 8 of Example 11, in Example 11, in which 4% by weight of phenoxyethyl carbonate and the compound of Example 1 were mixed, the melting point of the first heating was 193.85 degrees Celsius, It can be seen that the melting point during the second heating is 193.35 degrees Celsius. That is, the difference is about 3.23 degrees in the primary heating and 0.73 degrees in the secondary heating.

9 shows that the melting point of the first heating was 185.10 degrees Celsius and the melting point of the second heating was 189.10 degrees Celsius when the phenoxyethyl carbonate was mixed at 10% by weight in Example 15. These results, when the plasticizer is increased to 10%, it can be seen that the first 11.98 degrees, the second 4.98 degrees difference compared to Comparative Example 1 of 100% by weight polyketone.

Therefore, the composition of the present invention, in particular, it can be seen that the melting point at the time of the first heating is lowered to increase the fluidity and plasticization effect, and as shown in Example 7, there is almost no difference in melting point between the primary and secondary heating, It is expected to be particularly excellent in the residue recycling process during injection, and when the plasticizer content is increased as in Example 15, it can be seen that the plasticizing effect is further increased.

In the case of the twin screw type extruder generally used for extrusion, extrusion is produced by gradually raising the extrusion temperature from 170 degrees Celsius to 190 degrees Celsius initially. It is common. Therefore, while the polyketone composition of Comparative Example 1 is difficult to form due to the high melting point as described above, the polyketone composition of Examples 7, 11 and 15 has a low melting point, so that the extrusion process is smooth and the power consumption is reduced. It is possible to prevent unnecessary temperature rise during secondary processing.

This lowering of the melting point and the constant temperature of the primary and secondary heating, together with the MI measurement value demonstrates a good plasticizing effect.

Those skilled in the art to which the present invention pertains will be able to perform various applications and modifications within the scope of the present invention based on the above contents.

Claims (9)

A polyketone composition comprising 50 wt% to 99 wt% of a polyketone, and 1 wt% to 50 wt% based on the total weight of the composition, and at least one plasticizer selected from Formulas 1a and 1b:

(1a)

(1b)
Where
R ₁ and R ₃ are each independently OH, OCH ₃ , OCH ₂ OH, O (CH ₂ ) _n CH ₃ , O (CH ₂ ) _n CH ₂ OH, OC ₆ H ₅ , OC ₆ H ₄ OH, O ( CH ₂ ) _n C ₆ H ₅ , O (CH ₂ ) _n C ₆ H ₄ OH, O (CH ₂ ) _n C ₆ H ₄ CH ₂ OH, OC ₆ H ₁₁ , OC ₆ H ₁₀ OH, OC ₆ H ₁₀ CH ₂ OH, O (CH ₂ ) _n C ₆ H ₁₁ , O (CH ₂ ) _n C ₆ H ₁₀ OH or O (CH ₂ ) _n C ₆ H ₁₀ CH ₂ OH, where n is from 1 to 20 Natural number;
R ₂ is (CH ₂ ) _m , [(CH ₂ ) _m -C ₆ H ₄ ] _p , [(CH ₂ ) _m -C ₆ H ₁₀ ] _q , [(CH ₂ ) _a -X- (CH ₂ ) _b ] _s , [(CH ₂ ) _a -X- (CH ₂ ) _b -Y- (CH ₂ ) _c ] _t or [(CH ₂ ) _a C (CH ₃ ) ₂ (CH ₂ ) _{a '} -X- (CH ₂ ) _b C (CH ₃ ) ₂ (CH ₂ ) _{b '} ] _s ;
here,
m is a natural number from 1 to 20;
X and Y are independently of each other C ₆ H ₄ , C ₆ H ₁₀ , O, CO ₂ , OCO ₂ , O ₂ C Or NH;
a, a ', b, b' and c are each independently a natural number of 1 to 20;
p, q, s and t are each independently a natural number of 1 to 5,
R ₄ and R ₆ independently of one another are H, CH ₃ , CH ₂ OH, (CH ₂ ) _n CH ₃ , (CH ₂ ) _n CH ₂ OH, C ₆ H ₅ , C ₆ H ₄ OH, (CH ₂ ) _n C ₆ H ₅ , (CH ₂ ) _n C ₆ H ₄ OH, (CH ₂ ) _n C ₆ H ₄ CH ₂ OH, C ₆ H ₁₁ , C ₆ H ₁₀ OH, C ₆ H ₁₀ CH ₂ OH, ( CH ₂ ) _n C ₆ H ₁₁ , (CH ₂ ) _n C ₆ H ₁₀ OH, (CH ₂ ) _n C ₆ H ₁₀ CH ₂ OH, (CH ₂ ) _n OCO ₂ (CH ₂ ) _{n '} H or (CH _{2) n OCO 2 (CH 2} ) n ' , and OH, where, n and n' is a natural number of 1 to 20;
R ₅ is (CH ₂ ) _m , where m is a natural number from 1 to 20,
CH ₂ , (CH ₂ ) _n , (CH ₂ ) _m , C ₆ H ₅ , C ₆ H ₄ , C ₆ H ₁₁ And C ₆ H _{10 −} are substituted or unsubstituted structures, and in the case of substituted structures, at least one hydrogen is substituted with a C ₁ -C ₅ alkyl group. The method of claim 1, wherein the polyketone is a homopolymer comprising an ethylenically unsaturated monomer having a carbon monoxide and at least two carbon atoms represented by the following formula (2), or represented by the following formula (3) carbon monoxide, ethylene and at least A polyketone composition, characterized in that it is a linear alternating copolymer comprising an ethylenically unsaturated monomer having three carbon atoms:

(2)

(3)
Where
A is a first aliphatic hydrocarbon derived from an ethylenically unsaturated monomer having at least two carbon atoms;
u is 2 to 100;
v is 10 to 100, w is 1 to 50, and the ratio of v / w is 2 to 100. The polyketone composition according to claim 1, wherein R ₁ and R ₃ are each independently OCH ₃ or O (CH ₂ ) _n CH ₃ (a natural number of n = 1 to 5). The compound of claim 1, wherein R ₂ is (CH ₂ ) _m , [(CH ₂ ) _a -X- (CH ₂ ) _b ] _s or [(CH ₂ ) _a -X- (CH ₂ ) _b -Y- (CH ₂ ) _c ] _t polyketone composition. The compound of claim 1, wherein R ₄ and R ₆ are independently of each other, (CH ₂ ) _n CH ₂ OH, (CH ₂ ) _n OCO ₂ (CH ₂ ) _{n ′} H, or (CH ₂ ) _n OCO ₂ (CH _{2) n 'OH,} wherein, n and n' is a polyketone composition, characterized in that the natural numbers from 1 to 5. 5. The polyketone composition of claim 4, wherein X and Y are independently of each other O, CO ₂ , OCO ₂ or O ₂ C. The polyketone composition according to claim 1, wherein the molecular weight of the R ₂ moiety is in the range of 100 to 3,000. The polyketone composition according to claim 1, further comprising a plasticizer of formula (4):

(4)
Where
R ₇ is OH, OCH ₃ , O (CH ₂ ) _n CH ₃ , OC ₆ H ₅ , O (CH ₂ ) _n C ₆ H ₅ , OC ₆ H ₁₁ or O (CH ₂ ) _n C ₆ H ₁₁ , Where n is a natural number from 1 to 20;
R ₈ is CH ₃ , OH, CO ₂ H, OCH ₃ , O (CH ₂ ) _n CH ₃ , OC ₆ H ₅ , O (CH ₂ ) _n C ₆ H ₅ , OC ₆ H ₁₁ , O (CH ₂ ) _n C ₆ H ₁₁ , CO ₂ CH ₃ , OCO ₂ CH ₃ , CO ₂ (CH ₂ ) _n CH ₃ , OCO ₂ (CH ₂ ) _n CH ₃ , CO ₂ C ₆ H ₅ , OCO ₂ C ₆ H ₅ , CO ₂ (CH ₂ ) _n C ₆ H ₅ , OCO ₂ (CH ₂ ) _n C ₆ H ₅ , CO ₂ C ₆ H ₁₁ , OCO ₂ C ₆ H ₁₁ , CO ₂ (CH ₂ ) _n C ₆ H ₁₁ or OCO ₂ (CH ₂ ) _n C ₆ H ₁₁ Wherein n is a natural number from 1 to 20;
k is a natural number from 1 to 20. The method according to claim 8, wherein R ₇ is OCH ₃ , OCH ₂ CH ₃ or OC ₆ H ₁₁ , R ₈ is CH ₃ , OH or CO ₂ H, k is a natural number of 1 to 8 Ketone composition.

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