KR100458868B1 - Polyolefin and Polyolefin Copolymers with Carbamate Reactive Group and the Method of Manufacturing thereof - Google Patents

Abstract

The present invention relates to a polyolefin having a carbamate group, a polyolefin copolymer, and a method for producing the same. More particularly, by forming a carbamate group in a molecule of a polyolefin and a polyolefin copolymer, excellent physical properties are obtained even when mixed with dissimilar resins. The present invention relates to a polyolefin, a polyolefin copolymer having a carbamate group represented by the following Chemical Formula 1, and a method for producing the same.

[Formula 1]

In Formula 1, R is a hydrogen atom or a low molecular alkyl group having 1 to 5 carbon atoms, and Y is an alkyl, cycloalkyl or allyl group having 1 to 48 carbon atoms after removing the hydroxyl group from the monohydric alcohol.

The polyolefin and polyolefin copolymer having a carbamate group according to the present invention forms a small and uniform dispersed phase, so that the tensile strength and the impact strength are significantly increased compared to the blends between incompatible polymers, and excellent reactivity when blending between dissimilar resins It can be used as a compatibilizing agent of the incompatible interpolymer blend, and can also be used as an adhesive resin in coextrusion of thermoplastic resins.

Description

Polyolefin and Polyolefin Copolymers with Carbamate Group and Manufacturing Method Thereof {Polyolefin and Polyolefin Copolymers with Carbamate Reactive Group and the Method of Manufacturing E}

The present invention relates to a polyolefin having a carbamate group, a polyolefin copolymer and a method for producing the same. More specifically, by forming a carbamate group in a molecule of a polyolefin and a polyolefin copolymer, excellent physical properties can be expressed even when mixed with heterogeneous resins. It relates to a polyolefin and a polyolefin copolymer having a carbamate group represented by the following formula (1), and a method for producing the same.

[Formula 1]

In Formula 1, R is a hydrogen atom or a low molecular alkyl group having 1 to 5 carbon atoms, and Y is an alkyl, cycloalkyl or allyl group having 1 to 48 carbon atoms after removing the hydroxyl group from the monohydric alcohol.

In general, homopolymers have unique properties determined by their chemical structures, and in some cases, polymers having properties that share the properties of each homopolymer are often required.

For this reason, heterogeneous homopolymers have been conventionally used as polymer blends for the above-mentioned purposes by polymer blending. Thus, blends between two or three component polyolefin resins or their resins and air In the case of the blend of the blend, not only can the advantages of the respective polymers be combined, but the manufacturing method is simple and the required cost is low, and the amount of use is greatly increased in each industrial field.

However, in the case of blending an engineering resin such as polyamide or polyester which lacks compatibility between blend components in the preparation of the blend of the polyolefin and its copolymer, the adhesion between the dispersed phase and the continuous phase is insufficient, and phase separation Since it causes a large amount of workability is lowered as well as the physical properties of the blend is degraded there was a problem that does not fully exhibit the advantages of each mixed resin.

In order to compensate for these disadvantages, a method of using a block copolymer of blended resins as a compatibilizer has been introduced, but such a block copolymer has an advantage of forming a small phase of the blend or increasing compatibility. On the other hand, it does not give a strong adhesive force to the interface of the dispersed phase and the continuous phase of the mixed dissimilar resin, and because it is not easy to manufacture has a lot of problems, such as a large cost is consumed in the manufacturing apparatus and equipment.

In this regard, US Pat. Nos. 4,174,358, 3,668,274 and 3,972,961, Korean Patent No. 246147, etc., are reactive compatibilizers for incompatible interpolymer blends, such as maleic anhydride, carboxyl groups, epoxy groups or isocyanate groups in a molecule. The technique which solved the disadvantage in the said block copolymer using the polyolefin which comprised the functional group of or its copolymer was introduced.

Polyolefin resins or polyolefin copolymers having such functional groups have many advantages in terms of productivity, such as low manufacturing cost and simplified manufacturing equipment and equipment.

In addition, the commercialization method using the polyolefin resin or the polyolefin copolymer having the functional group reduces the interfacial tension due to the chemical reaction between the components during blending to form a small and uniform dispersed phase, as well as between the components compared to the method using a block copolymer As it has the advantage of giving strong adhesion between interfaces by chemical bonding, researches to actively use it have been actively conducted in recent years.

However, when the functional group used as the reactive compatibilizer for the incompatible polymer blend in the polyolefin and the polyolefin copolymer is maleic anhydride, carboxyl group or epoxy group, it reacts well with the amine group of the polyamide resin when blended with the dissimilar resin. It is difficult to effectively react with a hydroxyl group or a carboxyl group, and thus has been limited in many applications as a reactive compatibilizer. When the functional group is an isocyanate group, the reactivity is excellent but the storage stability is poor.

Accordingly, in the present invention, by forming a carbamate group in which isocyanate groups are blocked in the molecules of the polyolefin and polyolefin copolymers, chemical reactions with most functional groups such as hydroxy groups and carboxy groups, as well as amine groups of the heterogeneous resin blended, are used as incompatible polymer blends. The present invention provides a polyolefin and a polyolefin copolymer having a carbamate group and a method of preparing the same.

In addition, the present invention provides a polyolefin and a polyolefin copolymer having a carbamate group having excellent storage stability by imparting a decrease in interfacial tension due to a chemical reaction and a strong adhesion of the interface and blocking an isocyanate group, and a method of preparing the same.

The present invention relates to a polyolefin having a carbamate group, a polyolefin copolymer and a manufacturing method, and more particularly, by forming a carbamate group in a molecule of a polyolefin and a polyolefin copolymer so that excellent physical properties can be expressed even when mixed with heterogeneous resins. It relates to a polyolefin having a carbamate group represented by the following formula (1), a polyolefin copolymer and a method for producing the same.

In Formula 1, R is a hydrogen atom or a low molecular alkyl group having 1 to 5 carbon atoms, and Y is an alkyl, cycloalkyl or allyl group having 1 to 48 carbon atoms after removing the hydroxyl group from the monohydric alcohol.

First, a carbamate group represented by Chemical Formula 1 is prepared.

The carbamate group according to the present invention is mixed with an unsaturated compound having an amide group represented by the following formula (2) and a halogenated formic acid compound represented by the following formula (3) in a molar ratio of 1: 1.5, and sodium hydroxide is dissolved in 5 to 10% by weight of dioxane. The mixture is mixed with 200 kg of solvent (or 200 kg of hexane solvent in which 5-10 wt% of sodium ethoxide is dissolved), reacted at 30 ± 10 ° C. under nitrogen atmosphere for 4 hours, and then extracted under vacuum.

In Formula 2, R is a hydrogen atom or a low molecular alkyl group having 1-5 carbon atoms.

In Formula 3, X is preferably a halogenated atom, especially chlorine and bromine, and Y is an alkyl, cycloalkyl or allyl group having 1 to 48 carbon atoms after removing the hydroxyl group from the monohydric alcohol.

At this time, unsaturated compounds having an amide group represented by the formula (2) include methacrylamide, acrylamide, and the like. Halogenated formic compounds represented by the formula (3) include ethyl chloroformate, propyl chloroformate, benzyl chloroformate, and the like. Can be used.

Then, the polyolefin and polyolefin air having a carbamate group by free radical melt graft copolymerization by adding a carbamate group and a peroxide, which is a polymerization initiator, to the polyolefin and the polyolefin copolymer and extruding at a high temperature of about 220 ° C. Prepare coalescing.

Polyethylene, polypropylene, polystyrene and the like are used as polyolefins, and ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, and the like are used as polyolefin copolymers.

When the polyolefin resin and polyolefin copolymer having a carbamate group of the present invention prepared by the above-described method are mixed at a ratio of 5 to 90% (W / W) of the heterogeneous incompatible resin and resin amount mixed therewith, Effective commercialization will be achieved, and the blends thus prepared can be used extensively throughout the industry, from food packaging and packaging films requiring gas barrier properties to automotive parts such as gasoline fuel tanks and the electronics industry. In addition, when co-extruded polyolefin resin, engineering resin, etc., it is possible to give very excellent adhesive force when used as an adhesive resin of the interface.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Test Examples.

Example 1 Preparation of Ethylene-Propylene-Diene Terpolymer Having Carbamate Group

4.26 kg of methacrylamide and 5.43 kg of ethyl chloroformate were mixed in a 200 kg dioxane solvent in which 14.4 kg of sodium hydroxide was dissolved, and reacted for 4 hours while maintaining a temperature of 30 ° C. under a nitrogen atmosphere. The mate groups are synthesized and then extracted under vacuum.

20 kg of an ethylene-propylene-diene terpolymer having a number average molecular weight of 20,500 and 0.2 kg of dicumyl peroxide are mixed with 1 kg of a carbamate group represented by Chemical Formula 4, followed by extrusion at an extruder to maintain a temperature of 220 ± 2 ° C. An ethylene-propylene-diene terpolymer having a carbamate group represented by 4 was prepared.

Example 2 Preparation of Low Density Polyethylene Resin Having Carbamate Group

10.4 kg of acrylamide and 5.43 kg of ethyl chloroformate are mixed in a 200 kg dioxane solvent in which 14.4 kg of sodium hydroxide is dissolved, and reacted for 4 hours while maintaining a temperature of 30 ° C. under a nitrogen atmosphere, and a carbamate represented by the following formula (5) The groups are synthesized and then extracted under vacuum.

1 kg of carbamate group represented by Formula 5 is mixed with 20 kg of low-density polyethylene resin having a number average molecular weight of 23,500 and 0.2 kg of dicumyl peroxide, and then extruded by maintaining the temperature of 220 ± 2 ℃ in an extruder A low density polyethylene resin having a mate group was prepared.

Example 3 Preparation of High Density Polyethylene Resin Having Carbamate Group

10.4 kg of acrylamide and 5.43 kg of propyl chloroformate are mixed in 200 kg of hexane solvent in which 14.4 kg of sodium ethoxide is dissolved, and reacted for 4 hours while maintaining the temperature of 30 ° C. under a nitrogen atmosphere. The carbamate group is synthesized and then extracted under vacuum.

1 kg of carbamate group represented by Chemical Formula 6 is mixed with 20 kg of high-density polyethylene resin having a number average molecular weight of 26,000 and 0.2 kg of dicumyl peroxide, and then extruded by maintaining the temperature of 220 ± 2 ° C. in an extruder. A high density polyethylene resin having a mate group was prepared.

Example 4 Preparation of Blend

A mixture of 50: 50% (W / W) of an ethylene-propylene-diene terpolymer having a carbamate group prepared in Example 1 and a conventional ethylene-propylene-diene terpolymer having no carbamate group; Nylon 10 resin having a number average molecular weight of 17,500 was mixed at 10: 90% (W / W) to prepare a blend, and then extruded, cooled, and solidified in an extruder while maintaining a temperature of 250 ± 2 ° C. It was cut in the state.

Example 5 Preparation of Blend

A mixture of a low density polyethylene resin having a carbamate group prepared in Example 2 and a conventional low density polyethylene resin having no carbamate group at 50: 50% (W / W), and a polyethylene terephthalate resin having a number average molecular weight of 22,500 20: 80% (W / W) and 80: 20% (W / W) were mixed to prepare a blend, and then extruded, cooled, and solidified in an extruder while maintaining a temperature of 290 ± 2 ° C. Cut into chips.

Example 6 Preparation of Blend

A mixture of a low density polyethylene resin having a carbamate group prepared in Example 2 and a conventional low density polyethylene resin having no carbamate group at 50: 50% (W / W), and a polycarbonate resin having a number average molecular weight of 19,000 20: 80% (W / W) and 80: 20% (W / W) were mixed to prepare blends, and then extruded, cooled, and solidified in an extruder at a temperature of 250 ± 2 ° C. It was cut in the state.

Example 7 Preparation of Blend

A mixture of a high density polyethylene resin having a carbamate group prepared in Example 3 and a general high density polyethylene resin having no carbamate group at 50: 50% (W / W), and a polyacetal resin having a number average molecular weight of 21,000 Blends were prepared by mixing 20: 80% (W / W) and 80: 20% (W / W), respectively, and then extruded, cooled, and solidified in an extruder while maintaining a temperature of 220 ± 2 ° C. It was cut in the state.

Example 8 Preparation of Blend

A mixture of a high density polyethylene resin having a carbamate group prepared in Example 3 and a general high density polyethylene resin having no carbamate group at 50: 50% (W / W), and a melt index of 3.5 and a vinyl alcohol mole fraction 68% high density polyethylene resins were mixed by 20: 80% (W / W) and 80: 20% (W / W), respectively, to prepare blends, and then they were maintained at a temperature of 220 ± 2 ° C. in an extruder. Extruded, cooled and solidified to cut into chips.

Comparative Example 1 Preparation of Blend

After blending a conventional ethylene-propylene-diene terpolymer with a nylon 6 resin having a number average molecular weight of 17,500 at 10: 90% (W / W) to prepare a blend, they were maintained at a temperature of 250 ± 2 ° C. in an extruder. Extruded in one state, cooled and solidified and cut into chips.

Comparative Example 2 Preparation of Blend

20: 80% (W / W) and 80: 20% (W / W) of a conventional low density polyethylene resin and a polyethylene terephthalate resin having a number average molecular weight of 22,500 were respectively mixed to prepare a blend. Extrusion, cooling, and solidification were carried out while maintaining a temperature of ± 2 ° C, and cut into chips.

Comparative Example 3 Preparation of Blend

After blending a conventional low density polyethylene resin and a polycarbonate resin having a number average molecular weight of 19,000 with 20: 80% (W / W) and 80: 20% (W / W), respectively, the blends were prepared, and then 250 ± 2 Extrusion, cooling, and solidification were carried out while maintaining the temperature at 占 폚, and cut into chips.

Comparative Example 4 Preparation of Blend

20: 80% (W / W) and 80: 20% (W / W) of a mixture of a conventional high density polyethylene resin and a polyacetal resin having a number average molecular weight of 21,000, respectively, are mixed to prepare a blend, and then they are 220 ± 2 in an extruder. Extrusion, cooling, and solidification were carried out while maintaining the temperature at 占 폚, and cut into chips.

Comparative Example 5 Preparation of Blend

A blend is prepared by mixing a conventional high density polyethylene resin with a high density polyethylene resin having a melt index of 3.5 and a vinyl alcohol molar fraction of 68% at 20: 80% (W / W) and 80: 20% (W / W), respectively. After these, they were extruded in the state of maintaining the temperature of 220 ± 2 ° C. in an extruder, cooled and solidified, and cut into chips.

Experimental Example 1

After freezing and crushing the blended water chips prepared from Examples 4 to 8 and Comparative Examples 1 to 5 in liquid nitrogen, the fracture surface was observed with a differential scanning electron microscope to detect 1,000 of the dispersed phases formed in the blend. The average size of the dogs is shown in Table 1.

Item Example Weight ratio Size of Dispersed Phase (㎛) Example 4 1: 9 1.4 Example 5 2: 8 1.3 8: 2 0.8 Example 6 2: 8 0.8 8: 2 0.7 Example 7 2: 8 0.4 8: 2 0.3 Example 8 2: 8 0.3 8: 2 0.6 Comparative Example 1 1: 9 10.1 Comparative Example 2 2: 8 10.5 8: 2 8.1 Comparative Example 3 2: 8 8.3 8: 2 8.4 Comparative Example 4 2: 8 6.6 8: 2 7.1 Comparative Example 5 2: 8 15.1 8: 2 13.5

As shown in Table 1, by mixing the polyolefin resin and polyolefin copolymer having a carbamate group of the present invention, the average size of the dispersed phase in the case of Examples 4 to 8 appeared to be very small as 0.2 to 1.3㎛, Comparative Example In the case of 1 to Comparative Example 5, the average size was shown to be up to 76 times larger than that of Examples 4 to 8 as 7.3 to 15.2 μm. As can be seen from the above results, when blending between heteropolymer resin having a hydroxyl group or a carboxy group as well as nylon 6 having an amine group as a polyamide resin, the polyolefin resin having a carbamate group and the polyolefin copolymer are added The interfacial tension between the and continuous phases was effectively reduced, indicating a good commercialization effect.

Experimental Example 2

-Tensile strength measurement test-

The blend water chips prepared from Examples 4 to 8 and Comparative Examples 1 to 5 were dried under reduced pressure at a temperature of 80 ° C. for 48 hours, and then injection molded into dumbbell-shaped specimens as defined in the tensile strength measurement test method of ASTM D638. After measuring the strength at break while stretching at a rate of 1.68cm / min, the same test was repeated 10 times the average value is shown in Table 2 below.

-Impact strength test-

The blend water chips prepared from Examples 4 to 8 and Comparative Examples 1 to 5 were dried under reduced pressure at a temperature of 80 ° C. for 48 hours, and then the width × vertical × thickness as defined in the test method for impact strength measurement of ASTM D256. After forming a specimen of 63.5 × 12.7 × 6.4mm, form a V-shaped groove of 2.5mm depth at the middle point of the specimen and measure the impact strength with an Izod impact tester. It is shown in Table 2 below.

Item Example Weight ratio Tensile Strength (kg / cm ² ) Impact Strength (kgcm / cm) Example 4 1: 9 468.1 10.1 Example 5 2: 8 137.6 4.3 8: 2 609.5 2.5 Example 6 2: 8 114.5 7.1 8: 2 462.5 5.5 Example 7 2: 8 102.7 4.1 8: 2 372.3 1.3 Example 8 2: 8 156.3 5.7 8: 2 532.7 4.7 Comparative Example 1 1: 9 225.3 2.5 Comparative Example 2 2: 8 81.1 2.6 8: 2 373.2 1.5 Comparative Example 3 2: 8 87.4 3.3 8: 2 292.6 2.6 Comparative Example 4 2: 8 62.4 2.5 8: 2 318.8 1.1 Comparative Example 5 2: 8 96.4 2.3 8: 2 284.9 1.5

As shown in Table 2, in the case of Examples 4 to 8 blended by mixing the polyolefin resin and polyolefin copolymer having a carbamate group of the present invention in the tensile strength as compared to Comparative Examples 1 to 5 It was found that 151% was high up to 217%, and it was found that the impact strength was remarkably increased from 138% to 450%.

The polyolefin and polyolefin copolymer having a carbamate group according to the present invention forms a small and uniform dispersed phase, so that the tensile strength and the impact strength are significantly increased compared to the blends between incompatible polymers, and excellent reactivity when blending between dissimilar resins The present invention can be used as a compatibilizer for incompatible interpolymer blends, and can also be used as an adhesive resin in coextrusion of thermoplastic resins.

Claims (10)

A polyolefin comprising a carbamate group compound represented by the following formula (1) in a molecule. [Formula 1] In Formula 1, R is a hydrogen atom or a low molecular alkyl group having 1 to 5 carbon atoms, and Y is an alkyl, cycloalkyl or allyl group having 1 to 48 carbon atoms after removing hydroxyl groups from a monohydric alcohol. 2. The polyolefin according to claim 1, wherein said polyolefin is polyethylene, polypropylene or polystyrene. The method of claim 1, wherein the carbamate group represented by Formula 1 is obtained by reacting an unsaturated compound having an amide group represented by Formula 2 with a halogenated formic compound represented by Formula 3 in a molar ratio of 1: 1.5 Polyolefin. [Formula 2] In Formula 2, R is a hydrogen atom or a low molecular alkyl group having 1-5 carbon atoms. [Formula 3] In Formula 3, X is preferably a halogen atom, especially chlorine and bromine, and Y is an alkyl, cycloalkyl or allyl group having 1 to 48 carbon atoms after removing hydroxyl groups from monohydric alcohol. The unsaturated compound having an amide group represented by Formula 2 is methacrylamide or acrylamide, and the halogenated formic compound represented by Formula 3 is ethylchloroformate, propyl chloroformate or benzyl chloroformate. Polyolefin characterized in that the. A method for producing a polyolefin having a carbamate group according to claim 1, wherein the carbamate group represented by Chemical Formula 1 of claim 1 is added to the polyolefin and free radical melt-grafted at 100 ° C to 300 ° C. A polyolefin copolymer comprising a carbamate group compound represented by the following formula (1) in a molecule. [Formula 1] In Formula 1, R is a hydrogen atom or a low molecular alkyl group having 1 to 5 carbon atoms, and Y is an alkyl, cycloalkyl or allyl group having 1 to 48 carbon atoms after removing hydroxyl groups from a monohydric alcohol. 7. The polyolefin copolymer according to claim 6, wherein the polyolefin copolymer is an ethylene-propylene copolymer or an ethylene-propylene-diene terpolymer. The method according to claim 6, wherein the carbamate group represented by Formula 1 is obtained by reacting an unsaturated compound having an amide group represented by Formula 2 with a halogenated formic compound represented by Formula 3 in a molar ratio of 1: 1.5. Polyolefin copolymer. [Formula 2] In Formula 2, R is a hydrogen atom or a low molecular alkyl group having 1-5 carbon atoms. [Formula 3] In Formula 3, X is preferably a halogen atom, especially chlorine and bromine, and Y is an alkyl, cycloalkyl or allyl group having 1 to 48 carbon atoms after removing hydroxyl groups from monohydric alcohol. The unsaturated compound having an amide group represented by Formula 2 is methacrylamide and acrylamide, and the halogenated formic compound represented by Formula 3 is ethylchloroformate, propyl chloroformate and benzyl chloroformate. Polyolefin copolymer, characterized in that. A method for producing a polyolefin copolymer having a carbamate group according to claim 6, wherein the carbamate group represented by Chemical Formula 1 of claim 6 is added to the polyolefin and free radical melt graft copolymerization is performed at 100 ° C to 300 ° C.