KR102093026B1 - Polyketone Composition Containing Plasticizer - Google Patents

Abstract

(1a)

(1b).The present invention is characterized in that it comprises 50 to 99% by weight of polyketone, and at least one plasticizer selected from the following formulas 1a and 1b, based on the total weight of the composition, 1 to 50% by weight of the polyketone composition. to provide.

(1a)

(1b).

Description

Polyketone composition containing plasticizers {Polyketone Composition Containing Plasticizer}

The present invention relates to a polyketone composition comprising a polyketone and a specific plasticizer.

Recently, interest in polymers of carbon monoxide and at least one ethylenically unsaturated monomer, particularly polyketone having a structure in which repeat units derived from carbon monoxide and repeat units derived from ethylenically unsaturated monomers are 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 material useful for various applications.

The high molecular weight of polyketone is considered to be useful as an engineering plastic material having higher mechanical and thermal properties and excellent economic efficiency. In particular, it has high wear resistance, so it can be used for parts such as automobile gears, high chemical resistance, lining materials for chemical transport pipes, various chemical bottles, etc. In addition, when an ultra-high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for fibers, it is possible to stretch at a high magnification and as a fiber having high strength and high elasticity oriented in the stretching direction, a reinforcement material for a belt, rubber hose, tire cord, or concrete reinforcement material It is a material that is very suitable for building materials and industrial materials.

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

U.S. Pat. A method for preparing a polymer of carbon monoxide and at least one ethylenically unsaturated monomer using a catalyst consisting of a bidentate ligand of phosphorus and phosphorus is disclosed, the disclosures of which are incorporated herein by reference.

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

In this regard, some prior arts propose blends with other polymers, etc., but it is true that certain limitations exist.

Accordingly, the present invention aims to solve the problems of the prior art as described above and the technical problems requested from the past.

The inventors of the present application have developed a composition in which a specific plasticizer is included in a polyketone through in-depth studies and various experiments, 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-resistant 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,

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

(1a)

(1a)

(1b)

(1b)

In the above formula,

R ₁ and R ₃ are independently of each other 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 1 to 20 A natural number, preferably 1 to 10;

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, preferably 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 from 1 to 20, preferably a natural number from 1 to 10;

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

R ₄ and R ₆ are independently of each other 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, where n and n' are natural numbers from 1 to 20, preferably 1 to 10;

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

CH ₂ above, (CH ₂ ) _n , (CH ₂ ) _m , C ₆ H ₅ , C ₆ H ₄ , C ₆ H ₁₁ And C ₆ H _{10 -} is a substituted structure or an 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 You can.

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

The ethylenically unsaturated monomer may have up to 20 carbon atoms, more specifically up to 10 carbon atoms. For example, aliphatic monomers such as ethane, propene, 1-butene, iso-butene, 1-hexene, 1-octene Or it may be an aryl aliphatic monomer containing an aryl substituent on another aliphatic molecule, and particularly an aryl substituent on an ethylenically unsaturated carbon atom. Examples of monomers of aryl aliphatic hydrocarbons among ethylenically unsaturated monomers are styrene, p-methyl styrene, p-ethyl styrene, and m-isopropyl styrene. Can be mentioned.

It is possible to use a number of different ethylenically unsaturated monomers in the same polymer, but in one specific example, the polyketone is represented by the following formula (2) and is homo including an ethylenically unsaturated monomer having at least two carbon atoms and carbon monoxide. It is a polymer, or a linear alternating copolymer comprising α-olefins, such as ethylene-based unsaturated monomers of carbon monoxide, ethylene and at least 3 carbon atoms, especially propylene, represented by the following formula (3).

(2)

(2)

(3)

(3)

In the above formula,

A is an aliphatic hydrocarbon derived from an ethylenically unsaturated monomer having at least 2 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 a 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 containing aliphatic hydrocarbons derived from ethylene for each unit containing such aliphatic hydrocarbons. In addition, the unit containing the aliphatic hydrocarbon derived from ethylene and the unit containing the aliphatic hydrocarbon are randomly found throughout the polymer chain.

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

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

As described above, a method of manufacturing such a polyketone is known from U.S. Patent No. 4,843,144, and 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 extrude and eject because it is gelled when left for a long time at over 240 degrees Celsius or short at 260 degrees Celsius. Is holding. In addition, since the fluidity is not secured during extrusion and injection, when manufacturing a film through blow molding after extrusion, the film must be thickened, making it difficult to control the thickness and making it difficult to manufacture the film due to brittle problems. Have.

On the other hand, the polyketone composition according to the present invention, as can also be seen in the experimental results to be described later, the melting point is lowered within the general molding temperature range to ensure fluidity, injection molding, extrusion molding, blow molding, etc. are possible and , The resulting molded products also do not have problems such as color change or brittleness. In particular, the polyketone composition according to the present invention has excellent heat resistance stability under molding conditions and fume generation can be minimized.

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

In Formula 1a, R ₁ and R ₃ may be, independently of each other, OCH ₃ or O (CH ₂ ) _n CH ₃ (a natural number of n = 1 to 5) in one preferred example, 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 100 to 3,000, more preferably 500 to 2,000.

In Formula 1b, R ₄ and R ₆ are, in one preferred example, 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, where n and n' can be a natural number from 1 to 5.

Since the content of the plasticizer in the polyketone composition of the present invention is 1% to 50% by weight based on the total weight of the composition as defined above, when the content of the plasticizer is too low, it may be difficult to achieve the purpose of lowering the melting point, Conversely, in the case of too many plasticizers, it is not preferable because molding may be difficult due to excessively high fluidity, and physical properties of the molded product may be deteriorated.

The content of the plasticizer may be preferably 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 Formula 4 may be further included in addition to the plasticizer of Formulas 1a and / or 1b, in a range in which the total content of the plasticizer does not deviate from the above range.

(4)

(4)

In the above formula,

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 , where n is a natural number from 1 to 20;

k is a natural number from 1 to 20.

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

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 can be a natural number from 1 to 8.

Other polymers known in the polyketone composition of the present invention may be further included, and since these other polymers are known in the art, detailed descriptions thereof will be omitted.

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

The molding may include, for example, injection molding, extrusion molding, blow molding, and the like, but is not limited to these.

As described above, the polyketone composition according to the present invention, the melting point is lowered within the general molding temperature range, it is possible to injection molding, extrusion molding, blow molding, etc., and the resulting molded products also have problems such as color change or brittleness. It has the advantage of being excellent in heat stability and minimizing fume generation in the molding process.

1 is a FT-IR analysis graph for the composite material of Example 1;
2 is a graph of FT-IR analysis for the composite of Example 3;
3 is a graph of FT-IR analysis for the composites of Example 7;
4 is a graph of FT-IR analysis for the composite of Example 11;
5 is a graph of FT-IR analysis for the composite of Example 14;
6 is a DSC analysis graph for 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, with reference to some embodiments according to the present invention will be described in more detail, the scope of the present invention is of course not limited by it.

[Example 1]

Toluene 500 g (5.4 mol), 176 g (2 mol) of 1,3-dioxolan-2-one, sesium hydroxide (CsOH) 5 g (0.03 mol) as a catalyst, 50 ml of water, and the cooling tube and In a reactor equipped with a stirrer and a mantle, one functional group was made into an alcohol form by reacting at a temperature of 80 degrees for 12 hours. The added water was removed by distillation at elevated temperature, and reacted at 150 degrees for 12 hours to complete the reaction, neutralized with 500 ml of 5% dilute hydrochloric acid solution, and extracted with a methylene dichloride solvent. Then, the solvent was distilled under reduced pressure to synthesize ethylene glycol dicarboxylic acid, and it was confirmed that carboxylic acid of the following 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 . Therefore, it can be confirmed that ethylene glycol dicarboxylic acid was synthesized.

As a plasticizer, 5% by weight of a compound and 95% by weight of polyketone (Hyosung Co., Ltd .; M 710) were mixed to prepare a polyketone composition.

[Example 2]

500 g (5.4 mol) of toluene, 204 g (2 mol) of 1,3-dioxan-2-one, and 5 g (0.03 mol) of sesium hydroxide (CsOH) as a catalyst, 50 ml of water, and the cooling tube and In a reactor equipped with a stirrer and a mantle, one functional group was made into an alcohol form by reacting at a temperature of 80 degrees for 12 hours. The added water was removed by distillation at elevated temperature, and reacted at 150 degrees 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, dicarboxylic acid ester was synthesized by distilling the solvent under reduced pressure, and it was confirmed that carboxylic acid of the following formula was produced using FT-IR.

As a plasticizer, 5% by weight of the compound and 95% by weight of polyketone (M 710) were mixed to prepare a polyketone composition.

[Example 3]

Methanol 500 g (15.6 mol) in 1,3-dioxolan-2-one 176 g (2 mol) and magnesium oxide (MgO) 2 g (0.05 mol) as a catalyst in a four-necked flask equipped with a stirrer and cooler After refluxing at 90 degrees for 6 hours, methanol was distilled off to obtain 2-hydroxyethyl methyl carbonate. 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 5% dilute hydrochloric acid Neutralized with and extracted with 500 ml of methylene chloride. Then, the dicarbonate ester compound was synthesized by distillation under reduced pressure, and the carbonate compound of the following formula was confirmed using FT-IR.

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

As a plasticizer, 5% by weight of the compound and 95% by weight of polyketone (M 710) were mixed to prepare a polyketone composition.

[Example 4]

Methanol 500 g (15.6 mol) in 1,3-dioxan-2-one 204 g (2 mol) and catalyst as magnesium oxide (MgO) 2 g (0.05 mol) in a four-neck flask equipped with a stirrer and cooler After refluxing at 90 degrees for 6 hours, methanol was distilled off to obtain 2-hydroxyethyl methyl carbonate. 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 5% dilute hydrochloric acid. Neutralized and extracted with 500 ml methylene chloride. Then, the dicarbonate ester compound was synthesized by distillation under reduced pressure, and the carbonate compound of the following formula was confirmed using FT-IR.

As a plasticizer, 5% by weight of the compound and 95% by weight of polyketone (M 710) were mixed to prepare a polyketone composition.

[Example 5]

Methanol 500 g (15.6 mol), 4-methyl-1,3-dioxolan-2-one 204 g (2 mol) and magnesium oxide (MgO) 2 g (0.05 mol) as a catalyst are equipped with a stirrer and cooler. After putting in a 4-neck flask and refluxing at 90 degrees for 6 hours, 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 refluxed at about 100 ° C for 10 hours to complete the reaction, followed by 5% dilute hydrochloric acid. Neutralized and extracted with 500 ml methylene chloride. Then, the dicarbonate ester compound was synthesized by distillation under reduced pressure, and the carbonate compound of the following formula was confirmed using FT-IR.

As a plasticizer, 5% by weight of the compound and 95% by weight of polyketone (M 710) were mixed to prepare a polyketone composition.

[Example 6]

Ethanol 719 g (15.6 mol), 204 g (2 mol) of 1,3-dioxan-2-one and 2 g (0.05 mol) of magnesium oxide (MgO) as a catalyst were added to a 4-neck flask equipped with a stirrer and a cooler. After refluxing at 100 degrees for 10 hours, ethanol was distilled off to obtain 3-hydroxypropyl-ethyl carbonate. 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, and refluxed at about 140 degrees for 12 hours to complete the reaction, followed by 5% dilute hydrochloric acid. Neutralized with and extracted with 800 ml of methylene chloride. Then, the dicarbonate ester compound was synthesized by distillation under reduced pressure, and the carbonate compound of the following formula was confirmed using FT-IR.

As a plasticizer, 5% by weight of the compound and 95% by weight of polyketone (M 710) were mixed to prepare a polyketone composition.

[Example 7]

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

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

As a plasticizer, 5% by weight of the compound and 95% by weight of polyketone (M 710) were mixed to prepare a polyketone composition.

[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 catalyst and xyl The reaction of 250 g of ren was carried out for 8 hours at 230 ° C using a flask equipped with a thermometer and a water removal device, and then unreacted cyclohexylmethanol 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.

As a plasticizer, 5% by weight of the compound and 95% by weight of polyketone (M 710) were mixed to prepare a polyketone composition.

[Example 9]

260 g (2.5 mol) of neopentyl glycol and 1 g (0.01 mol) of phosphoric acid as catalyst for 104 g (1 mol) of malonic acid were used for 10 hours at 230 ° C using a flask equipped with a thermometer and a water removal device. After the reaction proceeded, it was cooled to room temperature. Then, neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), washed with water and dehydrated, and then depressurized to remove unreacted neopentyl glycol that is not dissolved in water, and the dienepentyl malonate-based ester compound of the following formula Got

As a plasticizer, 5% by weight of the compound and 95% by weight of polyketone (M 710) were mixed to prepare a polyketone composition.

[Example 10]

As a catalyst for 414 g (1.5 mol) of dienepentyl malonate and 319 g (4.2 mol) of methylhydrogen carbonate obtained in Example 9, 1 g (0.01 mol) of phosphoric acid as a catalyst is attached with a thermometer and a generator for removing water. After the reaction was performed at 150 ° C for 12 hours, the cooled flask was cooled to room temperature. Neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), washed with water and dehydrated, and then depressurized to remove unreacted neopentyl glycol that was not dissolved in water to obtain a dienepentyl maleic dicarbonate-based ester compound of the following formula. Got.

As a plasticizer, 5% by weight of the compound and 95% by weight of polyketone (M 710) were mixed to prepare a polyketone composition.

[Example 11]

207 g (1.5 mol) of phenoxyethanol and 152 g (2 mol) of methylhydrogen carbonate are used as catalysts, and 0.5 g (0.005 mol) of phosphoric acid is used as a catalyst at 150 degrees using a flask equipped with a thermometer and a water removal device. After the reaction was performed for 12 hours, the mixture was cooled to room temperature. Then, neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), washed with water and dehydrated, and then depressurized to remove unreacted methylhydrogen carbonate that was not dissolved in water, and phenoxyethyl carbohydrate of the following formula Nate-based ester compounds were 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 . Therefore, 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 the polyketone (M 710).

[Example 12]

207 g (1.5 mol) of phenylhydrogen carbonate and 180 g (2 mol) of butanediol as catalyst, 0.5 g (0.005 mol) of phosphoric acid as a catalyst, using a flask equipped with a thermometer and water removal device, at 220 to 10 After the time reaction proceeded, it was cooled to room temperature. Then, neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), washed with water and dehydrated, and then distilled under reduced pressure to obtain 1-hydroxybutyl-phenylcarbonate, followed by 1-hydroxybutyl-phenylcarbonate 210 0.5 g (0.005 mol) of phosphoric acid as a catalyst for g (1 mol) and 114 g (1.5 mol) of methylhydrogen carbonate using a flask equipped with a thermometer and water removal device for 12 hours at 150 ° C After the reaction proceeded, it was cooled to room temperature. Then, neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), washed with water and dehydrated, and then depressurized to remove unreacted methylhydrogen carbonate that was not dissolved in water to remove butylphenyl carbonate ester of the formula System compounds.

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 the polyketone (M 710).

[Example 13]

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

As a plasticizer, 5% by weight of the compound and 95% by weight of polyketone (M 710) were mixed to prepare a polyketone composition.

[Example 14]

Ethylene glycol dicarboxylic acid ethylene dialcohol obtained in Example 13 and 590 g (1 mol) of methylhydrogen carbonate and 182 g (2.4 mol) of methylhydrogen carbonate as catalysts generated 0.5 g (0.005 mol) of phosphoric acid as a catalyst. The reaction was carried out at 150 ° C for 12 hours using a flask with a water removal device, and then cooled to room temperature. Then, neutralized with 5% sodium carbonate (Na ₂ CO ₃ ), washed with water and dehydrated, and then depressurized to remove unreacted methylhydrogen carbonate not dissolved in water to remove ethylene glycol dicarboxylate of the following formula. Diethyl carbonate compound was obtained.

5, OH strech peak does not appear, CH strech peak appears at 2850 cm ^-1 and 2950 cm ^-1 , C = O strech peak appears at 1740 cm ^-1 , and CO strech peak is 1250 cm ^-1 And 1120 cm ^-1 . Therefore, it can be confirmed that ethylene glycol dicarboxylate diethyl carbonate was synthesized.

As a plasticizer, 5% by weight of the compound and 95% by weight of polyketone (M 710) were mixed to prepare a polyketone composition.

[Example 15]

As a plasticizer, 10% by weight of phenoxyethyl carbonate obtained in Example 11 and 90% by weight of polyketone (M 710) were mixed to prepare a polyketone composition.

[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]

After 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, flow characteristics (Melt Flow Index: MI) were measured, and the results are shown in the following table. Provided in 1. MI was measured using WeedLab's Model WL 1400, and the reduction rate (%) was measured and left for 4 minutes at 230 degrees Celsius, and the first measurement was quantified and displayed for the initial 1 minute. The measurement is a result of observing the pellets obtained in the first measurement, finely cutting them, measuring them again, and quantifying the amount of flow for 1 minute, and observing each pellet color with the naked eye.

<Table 1>

As shown in Table 1, when compared with Comparative Example 1, it can be seen that the pellets prepared using the polyketone composition of the Examples 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]

DSC (Differential Scanning Calorimetry) 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, it can be seen that the melting points of the polyketone compositions of Examples 7, 11 and 15 were significantly lowered. On the other hand, in Comparative Example 1, it can be seen that the primary melting point is high when no plasticizer is added.

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

DSC analysis results of Figure 9 can be confirmed that in Example 15, when phenoxyethyl carbonate was mixed at 10% by weight, the melting point during primary heating was 185.10 degrees Celsius and the melting point during secondary heating was 189.10 degrees Celsius. These results, when the plasticizer was increased to 10%, compared to Comparative Example 1, which is 100% by weight of polyketone, the difference between the first 11.98 degrees and the second 4.98 degrees can be confirmed.

Accordingly, it can be seen that the composition of the present invention increases the fluidity by lowering the melting point during the primary heating, thereby achieving a plasticizing effect. Also, as in Example 7, there is almost no difference in the melting point between the primary and secondary heating. It is expected to be particularly excellent in the residue recycling process during injection, and it can be seen that the plasticizing effect is further increased when the plasticizer content is increased as in Example 15.

In the case of a twin screw type extruder that is generally used for extrusion molding, the extrusion temperature is gradually raised from 170 degrees Celsius to 190 degrees Celsius, and extrusion is produced. It is common. Therefore, the polyketone composition of Comparative Example 1 is difficult to form due to the high melting point as described above, while the polyketone composition of Examples 7, 11 and 15 has a low melting point to facilitate extrusion and reduce power consumption. It can be prevented from raising the temperature unnecessarily during secondary processing.

This melting point and the constant temperature of the primary and secondary heating explain that the plasticizing effect is well performed with the MI measurement value.

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.

Claims (9)

50 to 99% by weight of polyketone and 1 to 50% by weight of plasticizer,
The plasticizer includes a compound of Formula 1a, or a mixture of Formula 1a and Formula 1b,
The polyketone is represented by the following Chemical Formula 2 and a homopolymer comprising an ethylenically unsaturated monomer having carbon monoxide and at least 2 carbon atoms, or a Chemical Formula 3 having carbon monoxide, ethylene and at least 3 carbon atoms. A polyketone composition characterized by being a linear alternating copolymer comprising ethylenically unsaturated monomers:

(1a)

(1b)
In the above formula,
R ₁ and R ₃ are independently of each other 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 1 to 20 Is a 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 from 1 to 20;
p, q, s and t are each independently a natural number from 1 to 5,
R ₄ and R ₆ are independently of each other 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, where n and n' are natural numbers from 1 to 20;
R ₅ is (CH ₂ ) _m , where m is a natural number from 1 to 20,
CH ₂ above, (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 when substituted, one or more hydrogen Substituted with a C ₁ -C ₅ alkyl group,

(2)

(3)
In the above formula,
A is a first aliphatic hydrocarbon derived from an ethylenically unsaturated monomer having at least 2 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. delete The polyketone composition of claim 1, wherein R ₁ and R ₃ are, independently of each other, OCH ₃ or O (CH ₂ ) _n CH ₃ (a natural number of n = 1 to 5). The method according to 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, characterized in that. The method 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, where n and n' are polyketone compositions, characterized in that 1 to 5 is a natural number. The polyketone composition according to claim 4, wherein the X and Y are independently of each other O, CO ₂ , OCO ₂ or O ₂ C. The polyketone composition of claim 1, wherein the molecular weight of the R ₂ moiety is in the range of 100 to 3,000. The polyketone composition of claim 1, further comprising a plasticizer of Formula 4, wherein the content of the plasticizer of Formula 4 is 5 to 95 parts by weight based on 100 parts by weight of the remaining plasticizer:

(4)
In the above formula,
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 , where n is a natural number from 1 to 20;
k is a natural number from 1 to 20. The polysaccharide 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, and k is a natural number from 1 to 8. Ketone composition.

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