KR101155869B1 - Thermo-reversible Crosslinked elastomer and Method producing thereof - Google Patents

Abstract

The present invention uses a compound grafted with maleic anhydride (MA) to synthetic rubber or an olefin resin as a sole substrate or a mixed composition in which a urethane resin is mixed with the grafted compound. A thermally reversible crosslinkable elastomer composition, wherein the reactive amine compound and the metal oxides added to the base material form hydrogen bonding and ionic interaction between rubber or olefinic molecules, and The present invention relates to a method for producing an elastomer using the same, which has elasticity and mechanical properties similar to those of a crosslinked rubber, and exhibits thermo-reversible crosslinking by heat, so that it can be reused, and also used synthetic rubber or synthetic resin. When it is heated, it melts again and can be revulcanized It is possible to continuously process and produce by reusing general thermoplastics or rubber processing equipment such as machine, injection machine, calender, etc., and it has the advantages of excellent mechanical properties as well as elastic recovery. It is an advantage of the manufacturing method.

Thermoreversible Rubber, Maleic Anhydride, Graft, Synthetic Rubber, Olefin Resin, Reactive Amine Compound, Metal Oxide, Hydrogen Bond, Ion Bond, Recycling, Elasticity, Elasticity Resilience

Description

Thermoreversible crosslinked elastomer composition and method for producing elastomer using same

The present invention uses a compound grafted with maleic anhydride (MA) to synthetic rubber or an olefin resin as a sole substrate or a mixed composition in which a urethane resin is mixed with the grafted compound. Reactive amine compounds and metal oxides added to this substrate form hydrogen bonds and ionic bonds between rubber or olefinic molecules to have elastic and mechanical properties similar to those of crosslinked rubbers. The present invention relates to a thermoreversible crosslinkable elastomer composition and a method for producing an elastomer using the same, because the thermo-reversible crosslinking is performed by heat.

In general, rubber has elasticity to return to its original state when the shape and volume are deformed by the external force and then remove the force. The elasticity of the rubber deforms even if the external force is removed at any stage when the force is gradually increased. In order to increase the limit of the permanent deformation and to improve the mechanical properties because the remaining permanent deformation, the crosslinking of the network structure is formed by using a crosslinking agent such as sulfur or organic peroxide in the rubber composition. However, the crosslinked rubber composition exhibits thermosetting so that it is impossible to recycle.

Recycling of the existing rubber means that the rubber cured by resembling the molecular structure of the rubber compound does not melt again due to the nature of the crosslinked rubber, so it cannot be re-vulcanized and recycled like new rubber. It was simply pulverized, powdered and then recycled to the extent that it was mixed with new rubber and used.

Therefore, in order to overcome the disadvantages of such a rubber composition, at room temperature, the rubber has elasticity, which is a characteristic of rubber due to physical aggregation of hard segments, and at high temperature, physical agglomeration is melted to bring thermoplastic to recycle (Thermoplastic elastomer; TPE). ) Has been developed and used in the field of rubber applications, and recently, as environmental issues are most prominent throughout society and industry, research and development to replace rubber with TPE materials is actively progressing, and the field of application is gradually expanding.

Thermoplastic elastomers have the advantages of high productivity due to no difficult crosslinking process due to thermoplastics and the ability to use existing plastic processing equipment without modification, while being relatively heat resistant, durable and permanently compressed compared to conventional crosslinked rubbers with chemical crosslinking structure. Strain, elastic restoring force, scratch resistance, etc. are inferior and residual strain is large, resulting in stress relaxation or creep phenomenon. Thermoplastic vulcanizates (TPV) developed to compensate for these shortcomings are blends of soft rubber and hard plastic, but the soft rubber part is cross-linked to exhibit elasticity similar to that of conventional thermosetting rubber. Since plasticity is imparted by polypropylene (PP) or polyethylene (PE), which is mainly used for the filler, the filling rate of the filler is similar to that of general plastic, which makes it difficult to fill more than 30% by weight, and has a disadvantage of poor scratch resistance. .

Therefore, in order to solve the above problems, the thermally reversible crosslinked rubber is being developed, and such a thermally reversible crosslinked rubber has not been properly patented yet. However, such a conventional paper on the thermo-reversible hydrogen bonded crosslinked rubber, "Development of a fully recyclable thermo-reversible rubber" (quotation paper 1 Japanese Rubber Association, Yokohama Rubber Co., Ltd.) 75 (11), 482 (2002) by Shinnokawa, and "Thermal reversible crosslinked maleic ethylene / propylene rubbers grafted with anhydrous maleic and olefinic resins using hydrogen bonding and ionic interactions (thermoreversible crosslinking of maleated ethylene / propylene rubber using ionic interaction, hydrogen bonding and combination specifically) "(citation paper 2, MAJ van der Mee, JGP Goossens, rubber chemistry and technology, Vol 81, P96-109, 2007). For the same reason, it has not been commercialized yet.

That is, in the case of the above-cited papers 1, maleic anhydride graft rubber was prepared in a solution state, and then aliphatic amine and metal acetate were prepared through a low temperature reaction of 80 ° C. or lower, followed by thermoreversibility. As a method of obtaining rubber, there is a problem in that the manufacturing method is complicated as the rubber is prepared in a solution state, and the reaction time is long as it is synthesized through low temperature reaction. In order to form a bond, maleic anhydride graft EPDM was dissolved in a solution of toluene and isopropanol at 90/10, and then ZnAC ₂ (Zinc acetate dihydrate) and KAc (Potassium acetate) solution were added thereto. The rubber is neutralized and dried for several days at room temperature to induce ionic bonds. It is the production process is complicated and, because of the manufacturing process with the solution method is not available in conventional rubber processing equipment was the situation that not yet commercialized successfully.

Therefore, the present invention for solving the above problems is to use a commercially available maleic anhydride (MA) grafted synthetic rubber or olefin resin prepared by the prior art as the sole substrate or the graph As a substrate, a mixed composition obtained by mixing a urethane-based resin with a compound to be compounded is used as a substrate. It has a similar elastic and mechanical properties to the crosslinked rubber, and exhibits reversible reaction (thermo-reversible crosslinking) by heat at a temperature of 150 ~ 200 ℃ thermo-reversible crosslinkable elastomer composition, characterized in that the reuse is possible It is a problem to provide a method for producing an elastic body.

Therefore, due to the nature of the existing synthetic rubber or resin, the synthetic rubber or resin that is hardened to resemble the molecular structure of the compound is not melted again, so it cannot be recycled by re-vulcanization and recycling like a new rubber or a new synthetic resin. The synthetic rubber or synthetic resin was finely pulverized into powder and then recycled to the extent that it is simply mixed with a new rubber or a new synthetic resin, but the present invention is re-vulcanized while being melted again when heat is applied to the used rubber or synthetic resin. It is possible to continuously process and produce by reusing general thermoplastics or rubber processing equipment such as extruder, injection machine, calender, etc., and has excellent mechanical properties as well as elastic resilience and recycling of resources. Is a further object to provide a method for producing the reversible heat-cross-linkable elastomer composition using the same, and the elastic body, it characterized in that the composition and manufacturing gongbeopin having a horn characteristics.

The present invention for solving the above problems is 0.1 ~ reactive amine compound with respect to 100 parts by weight of maleic anhydride (MA) grafted synthetic rubber or olefin resin substrate prepared by a conventionally commercialized method The thermoreversible rubber composition characterized by mixing 12.0 parts by weight, 0.2-15.0 parts by weight of metal oxide, 0-500 parts by weight of inorganic filler and other additives is prepared as a means for solving the problem.

And the present invention is 20 to 80% by weight of a maleic anhydride (MA) grafted synthetic rubber or olefin resin base and urethane resin prepared by a conventionally commercialized method It is prepared by incorporating 0.05 to 20 parts by weight of reactive amine compound, 0.05 to 30 parts by weight of metal oxide, 0 to 500 parts by weight of inorganic filler, and other additives based on 100 parts by weight of the mixed composition substrate mixed with 20 to 80% by weight. The thermoreversible rubber composition characterized by the other problem solving means.

In addition, the present invention provides a method for producing a thermally reversible crosslinked elastomer,

(1) 0.1 to 12 parts by weight of a reactive amine compound and 1.0 to 2.0 parts by weight of a processing stabilizer based on 100 parts by weight of a synthetic rubber or olefin resin substrate using a banbury mixer or kneader capable of temperature control. Part, a first mixing step of mixing by adding 0.1 to 1.0 parts by weight of antioxidant;

(2) a second mixing step of adding 0 to 500 parts by weight of bicarbonate and 20 to 150 parts by weight of a plasticizer and mixing for 3 to 5 minutes to the mixture obtained in the first mixing step;

(3) a third mixing step of adding 0.2-15.0 parts by weight of a metal oxide to the mixture obtained in the second mixing step and mixing for 3-5 minutes;

Another method for solving the problem is a method for producing a thermally reversible crosslinked elastic body, characterized in that it is produced through.

In the above, synthetic rubber is used by selecting one from ethylene-propylene rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber,

The olefin resin is used by selecting one of low density polyethylene, linear low density polyethylene, high density polyethylene, ethylene copolymer,

The maleic anhydride grafted synthetic rubber or olefinic resin is a related art related to maleic anhydride grafting on synthetic rubber and olefinic resins: US Patent Nos. 2,970,129, 3,177,269, 3,270,090, 3,882,194, 3,886,227, 4,087,587, 4,087,588, 4,239,830, 4,298,712, 4,394,485, 6,221,928. % Grafted synthetic rubbers and olefins are commercially available.

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The reactive amine compound may be used by selecting one type from fatty primary or secondary amine, imidazole, triazole or amino-alcohol,

The metal oxide is preferably used by selecting one or more of zinc oxide, magnesium oxide, calcium oxide and potassium oxide.

According to the present invention, the reactive amine compound and the metal oxides added to the substrate form a hydrogen bond and an ionic bond between the synthetic rubber or the olefinic molecule to form elasticity similar to that of a crosslinked rubber. And mechanical properties, and exhibits thermo-reversible crosslinking by heat at a temperature of 150 ° C. or higher.

Therefore, the present invention can be re-vulcanized while being melted again when heat is applied to the used synthetic rubber or synthetic resin, thereby enabling continuous processing and production by reuse using common thermoplastic or rubber processing equipment such as an extruder, an injection molding machine, a calender, and the like. It is an advantage that it has an elastic recovery ability as well as excellent mechanical properties, so it is an advantage that it is a composition and manufacturing method having environmentally friendly characteristics in terms of recycling resources.

According to a feature of the present invention for solving the above problems, the present invention uses maleic anhydride (MA) grafted synthetic rubber or olefin resin prepared by a commercially available method as a sole substrate Or a mixed composition in which a urethane resin is mixed with the grafted compound as a substrate, and other additives such as a reactive amine compound, a metal oxide, an inorganic filler, an antioxidant, a plasticizer, and a processing stabilizer added to the substrate are added thereto. It can be prepared by dispersing and reacting at 150 ~ 200 ℃ for 5 ~ 15 minutes using a kneader, vanbari or twin extruder similar to the rubber processing process, and also used synthetic rubber or resin at heat of 150 ~ 200 ℃. By reversible reaction (thermo-reversible crosslinking) is characterized in that it is possible to reuse.

Hereinafter, with reference to the accompanying drawings, preferred embodiments of the present invention will be described in detail with reference to Figures 1 and 2, for the construction and operation that can be easily understood by those skilled in the art in the general synthetic rubber or synthetic resin composition manufacturing field in the detailed description Illustrations and references are briefly or omitted.

In the present invention, in preparing a reversible thermoreversible rubber composition, the substrate used in the present invention is largely divided into two types.

(1) 100 parts by weight of a maleic anhydride (MA) grafted synthetic rubber or olefin resin substrate prepared by a conventionally commercialized method alone

(2) or a mixture of 20 to 80% by weight of a maleic anhydride (MA) grafted synthetic rubber or olefin resin substrate prepared by a conventionally commercialized method and 20 to 80% by weight of a urethane resin 100 parts by weight of the substrate is used.

In the present invention, when the grafted compound base alone is used as in (1), it has elastic and mechanical properties similar to those of the crosslinked rubber, and thermally reversible crosslinking is performed at a temperature of 150 to 200 ° C. It is characterized by being reusable.

And when the urethane-based resin is mixed in the grafted compound substrate as in (2), the physical properties of the synthetic resin to be mixed according to the design conditions of the desired product with the same characteristics as in the compound of (1) It is characterized by being added.

When the mixed amount of the urethane resin mixed in the compound base material grafted in the mixed compound base material of (2) is less than 20% by weight, there is a concern that the physical properties of the mixed synthetic resin may not be properly expressed as the amount of the urethane resin is decreased. In addition, when the mixing amount of the urethane-based resin exceeds 80% by weight, there is a fear that the intrinsic properties of the thermoreversible composition may decrease as the mixing amount of the urethane-based resin is excessively added.

Synthetic rubber used in the present invention is preferably used by selecting one type from general-purpose rubbers such as ethylene-propylene rubber, isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, and the like. It is preferable to select and use 1 type from olefin resins, such as linear polyethylene, a high density polyethylene, an ethylene copolymer, etc.

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In addition, the compound bases of (1) and (2) for showing the properties of the thermoreversible crosslinkable elastomer composition according to the present invention are characterized in that the maleic anhydride (MA) is grafted as shown in the following Chemical Formula 1 do. In addition, the reaction conditions are reacted for 5 to 20 minutes at 150 ~ 200 ℃, the reaction is not well below 150 ℃ and over-reacted at 200 ℃ or more may lower the thermal reversibility.

(화학식 1)

(Formula 1)

And the description of the reactive amine compound and the metal oxide which is a compound added to the base material of the compounds (1) and (2) to exhibit the properties of the thermoreversible crosslinked elastomer composition is as follows.

The present invention preferably adds 0.05 to 20 parts by weight, more preferably 0.1 to 12 parts by weight, based on 100 parts by weight of the substrate (3) the reactive amine compound relative to 100 parts by weight of the substrate. When the amount of the reactive amine compound added is less than 0.1 part by weight, the synthetic rubber and olefin resin base grafted with maleic anhydride or the synthetic rubber and olefin resin grafted with maleic anhydride may be combined with a urethane resin. When hydrogen bond is not expressed in the mixed composition substrate, it does not show an increase in modulus such as a crosslinked rubber, and when it exceeds 12 parts by weight, the maleic anhydride is rapidly reacted with the grafted rubber and the olefin resin substrate. It is difficult to process.

The reactive amine compound is preferably selected from one of fatty primary or secondary amines, imidazole, triazole or amino-alcohol.

Specifically, the reactive amine compound may include a fatty primary amine having a structure of Formula 2 below, an imidazole having a structure of Formula 3 below, and a triazole having a structure of Formula 4 below. Or amino-alcohol (Amino-alcohol) having a structure of Formula 5 below.

CH ₃ (CH ₂ ) nX (Formula 2)

In Formula 2,

n is 10 to 20,

X is selected from the group consisting of -NH ₂ , -NHR and -NRR ', respectively, and R and R' are composed of hydrocarbons,

The hydrocarbon is selected from the group consisting of paraffinic, ethylene, acetylene, cycloparaffinic and naphthenic based.

(화학식 3)

(Formula 3)

In Formula 3,

X is selected from the group consisting of -H, -NH ₂ , -NHR and -NRR ', respectively, and R and R' are composed of hydrocarbons,

The hydrocarbon is selected from the group consisting of paraffinic, ethylene, acetylene, cycloparaffinic and naphthenic based.

(화학식 4)

(Formula 4)

X is selected from the group consisting of -H, -NH ₂ , -NHR and -NRR ', respectively, and R and R' are composed of hydrocarbons,

The hydrocarbon is selected from the group consisting of paraffinic, ethylene, acetylene, cycloparaffinic and naphthenic based.

X- (CH ₂ ) n-OH (Formula 5)

In Formula 5,

Where n is from 10 to 20,

X is selected from the group consisting of -NH ₂ , -NHR and -NRR ', respectively, R is hydroxy-C ₂ -C ₁₀ -alkyl, hydroxy-C ₂ -C ₄ -alkyl (oxa-C _2- C ₄ -alkyl) n wherein n is 1 to 5 and amino-C ₂ -C ₁₂ -alkyl.

The metal oxide is characterized in that it has a structure of formula (6).

Mt-O (Formula 6)

In Formula 6,

Mt is zinc or phosphorus.

Specifically, the metal oxide is preferably used by selecting one or more of zinc oxide, magnesium oxide, calcium oxide and potassium oxide.

In addition, according to the present invention, (4) the metal oxide is preferably added in an amount of 0.05 to 30 parts by weight, preferably 0.2 to 15 parts by weight based on 100 parts by weight of the substrate, and the amount of the metal oxide added is less than 0.2 parts by weight. In this case, it is difficult to expect improvement of physical properties due to metal bonding to the rubber and olefin resin substrates in which maleic anhydride is grafted, and when it exceeds 30 parts by weight, rubber and olefin resin in which maleic anhydride is grafted. Excessive metal ion reaction with and the degradation of the rubber composition.

Accordingly, in the thermoreversible crosslinkable elastomer composition according to the present invention, when the reactive amine compound and the metal oxides are added to the substrate, the thermoreversible rubber is ions between the synthetic rubber or the olefin-based molecule as shown in Scheme 1 below, and the hydrogen bond and the ions as shown in Scheme 2 below. Will be combined.

(Scheme 1)

(Scheme 2)

On the other hand, the thermally reversible rubber composition according to the present invention is a urethane-based compound using a compound grafted with maleic anhydride (MA) in a synthetic rubber or olefin resin as a sole substrate or the compound grafted Using a mixed composition mixed with a resin as a substrate, to prepare a rubber composition dispersed by adding a reactive amine compound, a metal oxide, an inorganic filler, and other additives to the substrate.

Since the various additives used in the present invention use additives which are usually added to the rubber composition or the synthetic resin composition for crosslinking, the various additives added in the present invention are not characteristics of the present invention.

As the inorganic filler, a material having a large function as a filler for increasing the rubber and improving physical properties of the inorganic compound may be generally used. As such representative examples, one or more selected from hard coal, bicarbonate, clay, silica, activated alumina, silica gel, amorphous aluminosilicate, and crystalline aluminosilicate may be used. Among them, the use of silica, amorphous aluminosilicate and crystalline aluminosilicate is particularly preferred.

Examples of the amorphous aluminosilicate include diatomaceous earth, kaolin, white clay, and the like, and examples of the crystalline aluminosilicate include about 34 or more natural zeolites and about 100 or more synthetic zeolites. Specific examples of natural zeolites include Analcime, chabaxite, Gmelinite, Epistilbite, Heirlandite, Stilibite, and Edingtonite. ), Mesolite, brosterite, fajasite, bizite, offretite, mordenite, and the like. A, zeolite L, zeolite T, zeolite KG, zeolite ZK-5, zeolite X, zeolite Y, zeolite ZSM-5, zeolite D, zeolite S, zeolite R, zeolite P, zeolite Z-21, zeolite S and the like.

The inorganic filler is 0 to about 100 parts by weight of the rubber and olefin resin substrate grafted with maleic anhydride or the mixed composition substrate with a urethane resin in a rubber and olefin resin grafted with maleic anhydride. 600 parts by weight, preferably 0 to 500 parts by weight is added. In the present invention, it is not necessary to use an inorganic filler according to the design conditions of the product to be molded, when the addition amount of the inorganic filler exceeds 500 parts by weight has a disadvantage that does not appear to improve the mechanical properties compared to the specific gravity increase.

And the other additives to prepare a thermoreversible rubber composition using processing stabilizers, antioxidants, plasticizers and the like.

In the present invention, the processing stabilizer may be used by selecting one or more of stearic acid, Zinc stearate. The processing stabilizer is 0.5 to 3.0 with respect to 100 parts by weight of the rubber and olefin resin bases grafted with maleic anhydride or the mixed composition base with urethane resins on the rubber and olefin resins grafted with maleic anhydride. Weight part Preferably it is preferable to add 1.0-2.0 weight part.

When the processing stabilizer is less than 1.0 part by weight, there is a disadvantage in that workability is lowered, and when it exceeds 3.0 parts by weight, mechanical properties such as elongation rate are lowered.

In the present invention, the antioxidant is the anti-aging agent Pentaerythrityl tetrakis [3- (3, 5-di-t-butyl-4-hydroxy phenyl) -propionate], Octadecyl 3- (3, 5-di-t-butyl 4-hydroxyphenyl) -propionate, 4,4'-Bis (alpha, alpha-dimethylbenzyl) di-phenylamine, polymerized 1,2-dihydro-2,2,4-trimethyl quinoline, 2,5-di-t- One or more of butyl-4-methylphenol, Hydroquinoline, N, N'-diphenyl-p-phenylenediamine, Tri (nonylatedphenyl) phosphite, 2-Mercaptobenziaidazole, and N-Cyclohexy thiophthal ilnide can be used. Antioxidant It is preferable to add 0.05-2.0 weight part preferably 0.1-1.0 weight part with respect to 100 weight part of base materials. If the antioxidant is less than 0.1 parts by weight it may show a tendency to deteriorate during processing, and if it exceeds 1.0 parts by weight, there is a disadvantage that the blooming occurs, the elongation is increased and the tensile strength is lowered.

In the present invention, the plasticizer may be used by selecting one or more of paraffin-based and naphthalene-based process oils. The plasticizer is 10 to 200% by weight based on 100 parts by weight of the maleic anhydride-grafted rubber and olefin resin substrate or the mixed composition of the maleic anhydride-grafted rubber and olefin resin with a urethane resin. It is preferable to add 20-150 weight part preferably. When the processing stabilizer is less than 10 parts by weight, there is a disadvantage in that the workability of the compound during processing is lowered. When the processing stabilizer is more than 150 parts by weight, the rubber composition is plasticized violently so that physical properties are lowered and elastic recovery power is reduced.

On the other hand, when explaining the method of manufacturing a thermo-reversible elastomer composition according to the invention having the composition as described above is as follows.

The present invention provides a method for producing a thermally reversible elastomer composition,

(1) 0.1 to 12 parts by weight of a reactive amine compound and 1.0 to 2.0 parts by weight of a processing stabilizer based on 100 parts by weight of a synthetic rubber or olefin resin substrate using a banbury mixer or kneader capable of temperature control. Part, a first mixing step of mixing by adding 0.1 to 1.0 parts by weight of antioxidant;

(2) a second mixing step of adding 0 to 500 parts by weight of bicarbonate and 20 to 150 parts by weight of a plasticizer and mixing for 3 to 5 minutes to the mixture obtained in the first mixing step;

(3) a third mixing step of adding 0.2-15.0 parts by weight of a metal oxide to the mixture obtained in the second mixing step and mixing for 3-5 minutes;

A thermoreversible elastic body is produced through.

The thermally reversible elastomer composition prepared as described above can be recycled because it has similar mechanical properties and elasticity as compared with the conventional rubber composition and has thermoplasticity at a high temperature, and can be molded in a conventional rubber injection molding machine and a plastic injection molding machine. It is done.

And since the specific features related to the substrate and various additives used in the present invention have already been described above, they are omitted here.

And the first mixing step is preferably mixed for 3 to 5 minutes while maintaining the speed of 30 ~ 90 rpm at a temperature of 150 ~ 200 ℃.

In the present invention, when the mixing conditions are less than the above range, various additives may not be properly mixed in the rubber raw material, and thus mechanical properties may deteriorate. When the mixing conditions are exceeded, various additives may be well mixed in the rubber raw material. On the contrary, there is a possibility that the mechanical properties decrease.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto.

1. Preparation of Thermoreversible Rubber Composition

The rubber composition of Examples 1 to 7 and the rubber composition of Comparative Examples 1 to 3 were prepared according to the blending ratio as described in Table 1 below.

Example 1

100 g of MA-g-EPDM (Royaltuf 498, MA-g-EPDM with 0.5 mol% grafted MA) was mixed with 0.1 g of reactive amine compound, 0.2 g of metal oxide, 2.0 g of stearic acid, and 1.0 g of antioxidant, at 180 ° C. The thermoreversible rubber composition was prepared by dispersing with a kneader for 10 minutes.

Example 2

To 100 g of MA-g-EPDM (Royaltuf 485, MA-g-EPDM with 1.0 mol% grafted MA), 12 g of reactive amine compound, 15 g of metal oxide, 2.0 g of stearic acid, and 1.0 g of antioxidant were mixed for 10 minutes at 180 ° C. The thermoreversible rubber composition was prepared through a process of dispersing using a kneader.

Example 3

200 g of inorganic filler and 50 g of plasticizer were added to 100 g of MA-g-EPDM (Royaltuf 485, MA-g-EPDM grafted with 1.0 mol% of MA), 12 g of reactive amine compound, 15 g of metal oxide, 2.0 g of stearic acid, and 1.0 of antioxidant. The mixture was mixed with g and dispersed at 180 ° C. for 10 minutes using a kneader to prepare a thermoreversible rubber composition.

Example 4

Into 100 g of MA-g-EPDM (Royaltuf 485, MA-g-EPDM with 1.0 mol% grafted MA), 500 g of inorganic filler and 80 g of plasticizer were added, 12 g of reactive amine compounds, 15 g of metal oxides and 2.0 g of stearic acid, and antioxidants 1.0. The mixture was mixed with g and dispersed at 180 ° C. for 10 minutes using a kneader to prepare a thermoreversible rubber composition.

Example 5

Into 80 g of MA-g-EPDM (Royaltuf 485, MA-g-EPDM with 1.0 mol% grafted MA) and 20 g of LDPE, 500 g of inorganic filler and 80 g of plasticizer were added, 10 g of reactive amine compounds, 12 g of metal oxides and 2.0 g of stearic acid, 1.0 g of antioxidant was mixed and dispersed in a kneader at 180 ° C. for 10 minutes to prepare a thermoreversible rubber composition.

Example 6

20 g of MA-g-EPDM (Royaltuf 485, MA-g-EPDM with 1.0 mol% grafted MA) and 80 g of LDPE were charged with 500 g of inorganic filler and 80 g of plasticizer, 2 g of reactive amine compound, 5 g of metal oxide, and 2.0 g of stearic acid, 1.0 g of antioxidant was mixed and dispersed in a kneader at 180 ° C. for 10 minutes to prepare a thermoreversible rubber composition.

Example 7

Into 80 g of MA-g-EPDM (Royaltuf 485, MA-g-EPDM with 1.0 mol% grafted MA) and 20 g of TPU, 500 g of inorganic filler and 80 g of plasticizer were added, 10 g of reactive amine compounds, 12 g of metal oxides and 2.0 g of stearic acid, 1.0 g of antioxidant was mixed and dispersed in a kneader at 180 ° C. for 10 minutes to prepare a thermoreversible rubber composition.

Comparative Example 1

400 g of inorganic filler, 80 g of plasticizer was added to 100 g of EPDM rubber, and 5 g of reactive amine compound, 9 g of metal oxide, 1 g of stearic acid, 0.3 g of antioxidant, and other additives were mixed to prepare an uncrosslinked rubber composition.

Comparative Example 2

400 g of inorganic filler and 80 g of plasticizer were added to 100 g of EPDM rubber, 5 g of reactive amine compound, 9 g of metal oxide, 1 g of stearic acid, 0.3 g of antioxidant and 1.0 g of sulfur, and 2.5 g of vulcanization accelerator were mixed to disperse and crosslinked. A rubber composition was prepared.

Comparative Example 3

An inorganic filler 200g and a plasticizer 50g were added to 100g of a thermoplastic vulcanized rubber L2K70N, 0.3g of an antioxidant was mixed and dispersed using a kneader at 180 ° C. for 10 minutes to prepare a rubber composition.

                                                     (Unit: g) division
Example Comparative example One 2 3 4 5 6 7 One 2 3 MA-g-EPDM ¹⁾ 100 - 100 100 80 20 80 - - - MA-g-EPDM ²⁾ - 100 - - - - - - - - LDPE ³⁾ - - - - 20 80 - - - - TPU ⁴⁾ - - - - - - 20 - - - EPDM ⁵⁾ - - - - - - - 100 100 - TPV ⁶⁾ - - - - - - - - - 100 Heavy ⁷⁾ - - 200 500 500 500 500 400 400 200 Process oil ⁸⁾ - - 50 80 80 80 80 80 80 50 Reactive amine compounds ⁹⁾ 0.1 12.0 12.0 12.0 10.0 2.0 10.0 5 5 - Metal oxide ¹⁰⁾ 0.2 15.0 15.0 15.0 12.0 5.0 12.0 9 9 - Stearic acid 2.0 2.0 2.0 2.0 2.0 2.0 2.0 One One - Antioxidant ¹¹⁾ 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.3 0.3 0.3 sulfur - - - - - - - - 1.0 - Vulcanization accelerator (1) ¹²⁾ - - - - - - - - 1.5 - Vulcanization Accelerators (1) ¹³⁾ - - - - - - - - 1.0 - 1) Royaltuf 498, graft ratio, 0.5%: Chemtura, USA
Royaltuf 485, graft ratio, 0.5%: Chemtura, USA
LDPE 722, Hanwha Petrochemical
4) Skythane S 190A, SK Chemical
5) KEP-270, Kumho Petrochemical
6) Thermoprene L2K70, Hwaseung Material
7) Heavy calcium carbonate, Lexem
8) P-3, Unchanged Petroleum
9) Dodecyl amine
10) Zinc Oxide
11) Songnox-1076, Songwon Chemical
12) bis (2-benzothiazole) disulfide
13) tetramethylthiuram monosulfide

2. Evaluation of Thermoreversible Rubber Composition

Rubber compositions prepared by Examples 1 to 7 and Comparative Examples 1 to 3 were subjected to the property test in the following manner to evaluate the mechanical properties of the composition, and the results are shown in Table 2 and FIG. 1. The loss modulus of each rubber composition was evaluated and the results are shown in FIG. 2.

1) Specific gravity: The average value was taken five times using an automatic specific gravity measuring device.

2) Hardness: Hardness was measured in accordance with ASTM D-2240 with an esker A hardness tester on the surface of the outsole.

3) Tensile strength: After making the outsole to about 3mm thickness, the test piece was made with a cutter (type 2) according to KS M6518 and the tensile strength and elongation were measured according to KS M6518. At this time, three test pieces were used for the same test.

4) Tear strength: The tear test was measured according to KS M6518, and the measurement speed was measured five times at 100 m / min.

5) Loss modulus: Loss modulus was measured in the range of -40 ~ 300 ℃ using DMA.

division Example Comparative example One 2 3 4 5 6 7 One 2 3 Longitude (A-type) 49-50 50-51 55-56 64-65 74-75 79-80 76-77 45-46 84-85 75-76 importance 0.88 0.88 1.58 1.63 1.62 1.60 1.63 1.63 1.69 1.53 The tensile strength
(kgf / cm ² ) 95 100 65 50 45 34 42 10 50 50 100% modulus
(000) 52 53 37 35 33 29 32 6 28 25 300% modulus
(000) 78 81 60 - - - - 7 45 47 Elongation
(%) 450 460 340 285 230 200 270 1200 500 350 Phosphorus strength
(kgf / cm) 52 55 32 28 20 18 24 7 25 30

As shown in Table 2, Example 1, Example 2 was found to be superior in mechanical properties compared to Comparative Example 1. In addition, it can be seen that Example 3 and Example 4 exhibited similar stress-strain behavior as Comparative Example 2 containing the same filler, and exhibited higher modulus than Comparative Example 3, which is a thermoplastic vulcanized rubber. Through these results, it was observed that the thermally reversible rubber composition prepared in Examples 1 and 2 has superior mechanical properties compared to Comparative Examples 1 and 3, which are unvulcanized rubber compositions. In addition, as shown in FIG. 2 through DMA analysis, as a result of evaluating the loss modulus of rubber compositions of Examples 3 and 3, Comparative Examples 1 and 2, Examples 3 and 4 were unvulcanized rubber. The loss modulus is relatively excellent compared to that of 1, which is similar to that of Comparative Example 2, which is a vulcanized rubber. Therefore, it can be seen that the embodiment is suitable for a thermoreversible rubber composition exhibiting elasticity.

As described above, the thermoreversible crosslinkable elastomer composition and its manufacturing method according to the preferred embodiment of the present invention have been described according to the above description and the drawings, which are merely described for example and do not depart from the spirit of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made therein.

1 is a photograph showing the stress-strain of the thermally reversible rubber of the embodiment and the rubber of the comparative example according to the present invention

Figure 2 relates to a photograph showing the storage modulus (Storage modulus) by DMA measurement of the thermoreversible rubber of the embodiment and the rubber of the comparative example according to the present invention.

Claims (11)

Maleic anhydride (MA) 0.1 to 12.0 parts by weight of reactive amine compound, 0.2 to 15.0 parts by weight of metal oxide, 0 to 500 parts by weight of inorganic filler, based on 100 parts by weight of grafted synthetic rubber or olefin resin substrate As a part and other additives, it is prepared by mixing 1.0 to 2.0 parts by weight of processing stabilizer, 0.1 to 1.0 part by weight of antioxidant, 20 to 150 parts by weight of plasticizer, The synthetic rubber is used by selecting one of ethylene-propylene rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber, The olefin resin is used by selecting one of low density polyethylene, linear low density polyethylene, high density polyethylene, ethylene copolymer, The maleic anhydride is grafted 0.5 to 1.0 mol% to 1 mol of synthetic rubber or olefin resin, The reactive amine compound is characterized by using one selected from fatty primary or secondary amine (fatty primary amine), imidazole (Imidazole), triazole (Ariazole) or amino-alcohol (Amino-alcohol) Thermoreversible Rubber Composition. Maleic anhydride (MA) Reactive amine compound 0.05 with respect to 100 parts by weight of the mixed composition substrate mixed with 20 to 80% by weight of the grafted synthetic rubber or olefin resin substrate and 20 to 80% by weight of the urethane resin. -20 parts by weight, 0.05-30 parts by weight of metal oxide, 0-500 parts by weight of inorganic filler, and other additives, 1.0 to 2.0 parts by weight of processing stabilizer, 0.1 to 1.0 parts by weight of antioxidant, 20 to 150 parts by weight of plasticizer But The synthetic rubber is used by selecting one of ethylene-propylene rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber, The olefin resin is used by selecting one of low density polyethylene, linear low density polyethylene, high density polyethylene, ethylene copolymer, The maleic anhydride is grafted 0.5 to 1.0 mol% with respect to 1 mol of synthetic rubber or olefin resin, The reactive amine compound is characterized by using one selected from fatty primary or secondary amine (fatty primary amine), imidazole (Imidazole), triazole (Ariazole) or amino-alcohol (Amino-alcohol) Thermoreversible Rubber Composition. delete delete delete delete delete The method according to claim 1 or 2, The metal oxide is a thermally reversible rubber composition, characterized in that one or more selected from the use of zinc oxide, magnesium oxide, calcium oxide, potassium oxide. The method according to claim 1 or 2, The inorganic filler is selected from one or more selected from hard coal, bicarbonate, clay, silica, activated alumina, silica gel, amorphous aluminosilicate, crystalline aluminosilicate and aluminum hydroxide. Thermo-reversible rubber composition characterized in. In the method of manufacturing a thermoreversible crosslinked elastomer, (1) 0.1 to 12 parts by weight of a reactive amine compound and 1.0 to 2.0 parts by weight of a processing stabilizer based on 100 parts by weight of a synthetic rubber or olefin resin substrate using a banbury mixer or kneader capable of temperature control. Part, a first mixing step of mixing by adding 0.1 to 1.0 parts by weight of antioxidant; (2) a second mixing step of adding 0 to 500 parts by weight of bicarbonate and 20 to 150 parts by weight of a plasticizer and mixing for 3 to 5 minutes to the mixture obtained in the first mixing step; (3) a third mixing step of adding 0.2-15.0 parts by weight of a metal oxide to the mixture obtained in the second mixing step and mixing for 3-5 minutes; Manufactured through The first mixing step is a method for producing a thermoreversible crosslinked elastomer, characterized in that for 3 to 5 minutes mixing while maintaining a speed of 30 ~ 90 rpm at a temperature of 150 ~ 200 ℃. delete

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