KR101527563B1 - Supramolecular network thermo-reversible crosslinked elastomer having heat-resistant, chemical-resistance, high mechanical properties - Google Patents

Abstract

The present invention relates to a process for producing a non-ionic surfactant, which is capable of ionizing an ethylene-propylene-propylene rubber compound grafted with an unsaturated carboxylic acid, alone or in combination, to form stronger supramolecular ionic interactions, Amide type supramolecular thermally reversible crosslinked elastomer having excellent heat resistance, chemical resistance, mechanical strength and permanent compression strain, which is improved not only in physical properties such as mechanical strength and permanent compression toughness but also in heat resistance and chemical resistance, ≪ / RTI >

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an amide-based supramolecular thermally reversible crosslinked elastomer composition having excellent heat resistance, chemical resistance, mechanical strength and permanent compression strain,

The present invention relates to a process for producing a non-ionic surfactant, which is capable of ionizing an ethylene-propylene-propylene rubber compound grafted with an unsaturated carboxylic acid, alone or in combination, to form stronger supramolecular ionic interactions, Amide type supramolecular thermally reversible crosslinked elastomer having excellent heat resistance, chemical resistance, mechanical strength and permanent compression strain, which is improved not only in physical properties such as mechanical strength and permanent compression toughness but also in heat resistance and chemical resistance, ≪ / RTI >

Generally, rubber has the elasticity to return to the original state when the shape and volume are deformed by the external force and then the force is removed. The elasticity of the rubber gradually increases the force, The remaining causes permanent deformation.

Therefore, in order to improve the limit of permanent deformation and the mechanical properties as described above, 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 and thus has a disadvantage that it can not be recycled. That is, due to the nature of the crosslinked rubber, the molecular structure of the rubber compound is retreated and cured, and the rubber is not melted again, so that it is newly melted and can not be recycled again like a new rubber.

Therefore, conventionally, in order to recycle the rubber, the used rubber was finely pulverized and powdered and then merely recycled to the new rubber.

On the other hand, in order to overcome the disadvantages of the rubber composition as described above, the thermoplastic elastomer which has the elasticity of the rubber due to the physical agglomeration of the hard segment at room temperature and the physical aggregation melts at the high temperature, ; TPE) has been developed and used in rubber applications. In recent years, environmental problems have been highlighted most in society and industry, and research and development has been actively carried out to replace rubber with TPE .

The thermoplastic elastomer is advantageous in that it has high productivity because there is no complicated crosslinking process due to its thermoplastic nature and can be used without modification of existing plastic processing equipment. On the other hand, compared with conventional crosslinked rubber having a chemical crosslinking structure, the thermoplastic elastomer has relatively high heat resistance, durability, The compressive strain, the elastic restoring force, and the scratch resistance are poor, and the residual strain is large, so that the stress relaxation and creep phenomenon are exhibited.

Thermoplastic vulcanizates (TPV), developed to overcome these shortcomings, are blends of soft rubber and hard plastic, but they are materials that exhibit resilience similar to conventional thermosetting rubber due to the cross-linking of soft rubber parts, (PP) or polyethylene (PE), which is mainly used for the rubber composition of the present invention, the packing ratio of the filler is low similarly to general plastics, It has a disadvantage of bad strain.

Accordingly, as a solution to the above-mentioned problem, what is being developed is the formation of a hydrogen bond, an ionic bond, or two bonds at the same time by using a supramolecular network control technique between rubber molecules, Thermally reversible crosslinked rubber which can be reprocessed at a temperature above the melting point of the thermotropic crosslinked rubber, and some patents have been filed for such a thermally reversible crosslinked rubber.

In the above-described research and development, there has been proposed a technique for "thermoplastic vulcanizing rubber obtained from EPDM or conjugated diene rubber and isobutylene rubber" in Patent Document 1, but the thermoplastic vulcanization rubber is partially crosslinked The rubber composition contains about 10 to 90 parts by weight of the combined rubber blend. The rubber blend is thermoplastic and develops a modulus similar to that of the vulcanized rubber. However, it has a problem in that the elastic restoring force is deteriorated due to the rubber composition of the partially crosslinked rubber.

Patent Document 2 proposes a technique for "a thermoplastic vulcanized rubber having a predetermined morphology for restoring optimum elasticity ", and the above-mentioned technique is based on the technique of controlling the continuous plastic material between the adjacent crosslinked rubber particles, However, when the hard plastic material is reduced in order to increase the resilience, the mechanical properties are relatively decreased. When the hard plastic material is reduced, the elasticity is decreased.

Patent Document 3 proposes a thermally reversible elastomer which forms a hydrogen bond by using a heterocyclic compound containing nitrogen in a synthetic rubber and a method of manufacturing the same. However, due to the method of hydrogen bond formation, The modulus is low.

Patent Document 4 proposes a technique for unsaturated carboxylic acid graft compound derivatives using a hydroxylamine ester as an ethylene compound. The patent discloses that the unsaturated carboxylic acid is used at a ratio of 0.5 20wt%. It has thermo-reversibility due to hydrogen bonding and has a disadvantage of low elastic recovery and low modulus.

On the other hand, Patent Document 5 discloses that a compound obtained by grafting a synthetic rubber or an olefin resin using maleic anhydride (MA) as a single base material, or by mixing a mixture obtained by mixing the grafted compound with other resin Characterized in that the composition is used as a substrate and the reactive amine compound and metal oxides added to the substrate form hydrogen bonding and ionic interaction between rubber or olefinic molecules The crosslinked structure of the patent is divided into hydrogen bonds and ionic interactions by ion clusters, and hydrogen bonds due to amine compounds are bonded to the crosslinked rubber Although the bond strength is weaker than the covalent bond, The graft ratio of the unsaturated acid anhydride having a high reactivity, such as maleic anhydride, is less than 2.0%. Therefore, the cross-linking of the crosslinking agent It is difficult to obtain the permanent compression strain at the level of the crosslinked rubber as the heat-reversible crosslinked composition.

Compounds prepared by the reactive extrusion method using an unsaturated acid anhydride such as maleic anhydride have a high viscosity of the rubber, resulting in severe heat generation during grafting and a marked deterioration in physical properties during repetitive rework, There was a problem.

In order to solve the above problems, the applicant of the present invention has previously filed a patent application entitled " Supramolecular thermally reversible crosslinkable elastomer composition having excellent mechanical strength and permanent compression strain and method for producing elastomer using the same " have.

Patent Document 6 discloses a process for producing a grafting rubber compound having a high graft ratio by using an unsaturated carboxylic acid, peroxide, and an antioxidant having high reaction stability compared to an unsaturated acid anhydride in an ethylene-propylene rubber (Ionic Interaction) by using ionizable metal salts alone or in combination to produce reversible reaction by heat at a temperature of 150 ° C. or higher while having elasticity and mechanical properties similar to those of a crosslinked rubber thermo-reversible crosslinking, and thus can be reused, and even when repeatedly used, the physical strength such as mechanical strength and permanent compression toughness hardly appears.

Accordingly, the applicant of the present invention has proposed an amide-based thermally reversible crosslinkable elastomer composition which improves not only the physical properties such as mechanical strength and permanent compression toughness but also heat resistance and chemical resistance by improving the above-mentioned Patent Document 6, and production of an elastic body using the same The present invention has been completed.

Patent Document 1: Korean Patent Laid-Open No. 10-1997-0027193 entitled "Thermoplastic vulcanized rubber obtained from EPDM or conjugated diene rubber and isobutylene rubber" Patent Document 2: Korean Patent Laid-Open No. 10-2002-0033732 entitled "Thermoplastic vulcanized rubber having a morphology set for optimum elastic recovery" Patent Document 3: U.S. Patent No. 6,746,562 entitled "Methods of making and recycling rubber bodies bonded with a thermo-reversible, crosslinkable elastomer" Patent Document 4: U.S. Patent No. 6,900,268 entitled "Method of grafting ethylenically unsaturated carboxylic acid derivatives onto thermoplastic using hydroxylamine esters" Patent Document 5: Korean Patent Laid-Open Publication No. 10-2011-0067361 "Thermally reversible crosslinkable elastomer composition and method for producing an elastomer using the same" Patent Document 6: Korean Patent Registration No. 10-1270545 entitled " Supramolecular thermally reversible crosslinked elastomer composition having excellent mechanical strength and permanent compression strain, and method of producing elastomer using the same "

The present invention relates to a method for producing an elastomeric composition having a high mechanical strength and permanent compression strain and a method for producing an elastomer using the same, which is registered by the applicant of the present invention as a registered trademark (Registration No. 10-1270545) As a result, it is possible to form more intense supramolecular ionic interactions by using metal salts capable of ionizing an ethylene-propylene-propylene rubber compound grafted with an unsaturated carboxylic acid, Amide type supramolecular thermally reversible crosslinked elastomer having excellent heat resistance, chemical resistance, mechanical strength and permanent compression strain, which is improved not only in physical properties such as mechanical strength and permanent compression toughness but also in heat resistance and chemical resistance, Composition.

In addition, since the present invention can be continuously processed and produced by reusing the rubber or synthetic resin which has been used, by reusing it by using general thermoplastic plastic or rubber processing equipment such as extruder, injector, calender, etc., Heat resistance, chemical resistance, mechanical strength, and permanent compression strain, which are environmentally friendly in terms of recycling of resources, and to provide an amide-based supramolecular thermally reversible crosslinking-type elastomer composition excellent in heat resistance, chemical resistance, mechanical strength and permanent compression strain.

The present invention relates to a supramolecular thermally reversible crosslinkable elastomer composition,

3 to 10 parts by weight of a metal salt and 0.1 to 1.0 part by weight of an antioxidant are mixed with 100 parts by weight of a base composed of 60 to 90% by weight of a carboxylic acid graft ethylene-propylene rubber and 10 to 40% by weight of a polyamide resin Which is excellent in heat resistance, chemical resistance, mechanical strength and permanent compression strain, which is characterized in that it is a thermally reversible crosslinkable elastomer composition.

The carboxylic acid grafted ethylene-propylene rubber is prepared by adding 0.15 to 25 parts by weight of unsaturated carboxylic acid, 0.01 to 0.3 part by weight of peroxide and 0.01 to 1.0 part by weight of an antioxidant to 100 parts by weight of ethylene-propylene rubber It is preferable that the carboxylic acid is grafted at 0.1 to 15.0%.

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The present invention relates to a process for producing a non-ionic surfactant, which is capable of ionizing an ethylene-propylene-propylene rubber compound grafted with an unsaturated carboxylic acid, alone or in combination, to form stronger supramolecular ionic interactions, By mixing a polyamide-based resin, it has an effect of improving not only physical properties such as mechanical strength and permanent compression toughness but also heat resistance and chemical resistance.

In addition, since the present invention can be continuously processed and produced by reusing the rubber or synthetic resin which has been used, by reusing it by using general thermoplastic plastic or rubber processing equipment such as extruder, injector, calender, etc., , And has an effect of having environment-friendly characteristics in terms of recycling of resources.

1 is a flow chart showing a method for producing an elastic body using an amide-based supramolecular thermally reversible crosslinkable elastomer composition having excellent heat resistance, chemical resistance, mechanical strength and permanent compression strain according to an embodiment of the present invention

The present invention for achieving the above effects relates to an amide-based supramolecular thermally reversible crosslinkable elastomer composition which is excellent in heat resistance, chemical resistance, mechanical strength and permanent compression strain, and only the parts necessary for understanding the technical structure of the present invention are explained It should be noted that the description of other portions will be omitted so as not to obscure the gist of the present invention.

Hereinafter, the amide-based supramolecular thermally reversible crosslinkable elastomer composition having excellent heat resistance, chemical resistance, mechanical strength and permanent compression strain according to the present invention will be described in detail.

The present invention relates to a resin composition comprising 3 to 10 parts by weight of a metal salt and 0.1 to 1.0 part by weight of an antioxidant per 100 parts by weight of a substrate composed of 60 to 90% by weight of a carboxylic acid graft ethylene-propylene rubber and 10 to 40% by weight of a polyamide resin .

The carboxylic acid grafted ethylene-propylene rubber used in the present invention is a copolymer of 0.15 to 25 parts by weight of an unsaturated carboxylic acid represented by the following general formula (1) and 0.01 to 25 parts by weight of peroxide 0.01 To 0.3 parts by weight of an antioxidant and 0.01 to 1.0 part by weight of an antioxidant are added so that 0.1 to 15.0% of a carboxylic acid is grafted.

On the other hand, when the content of the unsaturated carboxylic acid is less than 0.15 parts by weight, the graft ratio is low and it is difficult to form a supramolecular bonding structure between molecules. When the content of the unsaturated carboxylic acid exceeds 25 parts by weight, the grafting reaction occurs excessively, A phenomenon appears.

When the content of the peroxide is less than 0.01 part by weight, the grafting reaction does not start well and the grafting rate is lowered. When the content of the peroxide is more than 0.3 part by weight, peroxide reacts with rubber molecules to cause gelation .

In addition, when the antioxidant is not added, the initiation reaction by the peroxide can be rapidly induced to proceed the graft reaction. However, if the peroxide content is increased, the gelation may be caused. Therefore, if the peroxide is used in an amount of 0.15 parts by weight or more, If the content of the antioxidant is less than 0.01 part by weight, the function may not be realized. If the amount is more than 1.0 part by weight, the antioxidant may lower the initiation reaction of the peroxide.

On the other hand, the carboxylic acid graft ethylene-propylene rubber as described above is mixed with a polyamide resin to be described later to form a base material, and 60 to 90% by weight is used for forming the base material. The carboxylic acid graft ethylene- When the amount of the rubber is less than 60% by weight, the improvement of the mechanical strength and the permanent compression strain may be insufficient. When the amount of the rubber is more than 60% by weight, the content of the polyamide resin is decreased to improve the heat resistance and chemical resistance There is a possibility that the effect becomes insufficient.

(Formula 1)

In Formula 1,

R is a hydrocarbon derivative containing a double bond such as CH3-CH = CH-, HOOC-CH = CH-, HOOC = CH- or HOOC-CH2-CCH-.

The polyamide resin used in the present invention is added to improve the heat resistance and chemical resistance of the supramolecular thermally reversible crosslinkable elastomer composition. The polyamide resin is mixed with the carboxylic acid graft ethylene-propylene rubber to form a base material, If the amount of the polyamide resin is less than 10% by weight, the effect of improving heat resistance and chemical resistance may be insufficient. When the amount of the polyamide resin is more than 40% by weight, The content of the ethylene-propylene rubber is decreased and the effect of improving the mechanical strength and the permanent compression strain may be insufficient.

The metal salt used in the present invention is one in which the base of the carboxylic acid grafted ethylene-propylene rubber exhibits the properties of the hypermolecular thermally reversible crosslinkable elastomer composition and has a structure represented by the following formula (2) or (3) use.

Mt- R (Formula 2)

In Formula 2,

Mt is Sodium, Ammonium, Calcium, Magnesium, Zinc and R is CH3- (CH2) 2n-COO-, wherein n is 6-13 ) and _{CH 3 (CH 2) nCH =} CH (CH 2) nCOO- ( where, n is from 3 to 10 Im) selected from the group consisting of and the like.

Mt- X (Formula 3)

In Formula 3,

Mt can be selected from the group consisting of sodium, ammonium, calcium, magnesium, zinc, potassium, pyridinium, quaternary ammonium, Is selected from Acetate, Carbonate, Chloride, Citrate, Cyanide, Nitrate, Oxide and so on.

In this case, the metal salt includes an organic metal salt or a fatty acid metal salt, and is used in an amount of 3 to 10 parts by weight based on 100 parts by weight of the carboxylic acid graft ethylene-propylene rubber base. When the amount of the metal salt is less than 3 parts by weight It is difficult to expect reduction of the permanent compression strain due to the formation of ion clusters on the carboxylic acid graft ethylene-propylene rubber base material. When the amount exceeds 10 parts by weight, excessive use of the carboxylic acid graft ethylene- And exhibits a phenomenon in which the mechanical properties are deteriorated drastically during repeated processing due to the metal ion reaction.

Thus, the carboxylic acid grafted ethylene-propylene rubber composition according to the present invention forms supramolecular ionic bonds as shown in the following Reaction Scheme 1 and, when a metal salt is added thereto, the ionic-bonded supramolecular thermally reversible crosslinking Shaped elastomer composition is produced.

         (Scheme 1) (Scheme 2)

In addition, in order to construct the supramolecular thermally reversible crosslinkable elastomer composition of the present invention, an antioxidant is added in addition to the metal salt, and the antioxidant used in the present invention is Pentaerythrityl-tetrakis [3- (3,5-di- -hydroxy phenyl) -propionate], Octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'- 2-dihydro-2,2,4-trimethyl quinoline, 2,5-di-t-butyl-4-methylphenol, Hydroquinoline, N, N'- diphenyl- N-Cyclohexy thiophthalinide, and combinations thereof.

On the other hand, the antioxidant is used in an amount of 0.1 to 1.0 part by weight based on 100 parts by weight of the carboxylic acid graft ethylene-propylene rubber base material. When the amount of the antioxidant is less than 0.1 part by weight, If it exceeds 1.0 part by weight, blooming may occur in the product, the elongation percentage may increase, and the tensile strength may decrease.

Hereinafter, a method for producing an elastic body using the supramolecular thermally reversible crosslinkable elastomer composition according to the present invention will be described with reference to FIG.

The present invention relates to a method for producing an elastic body using a supramolecular thermally reversible crosslinkable elastomer composition,

0.1 to 25 parts by weight of an unsaturated carboxylic acid, 0.01 to 0.3 part by weight of peroxide and 0.1 to 1.0 part by weight of an antioxidant are mixed with 100 parts by weight of an ethylene-propylene rubber base material at a temperature of 100 to 200 占 폚 using a twin extruder At a speed of 30 to 150 rpm for 3 to 15 minutes to prepare an ethylene-propylene rubber having a carboxylic acid of 0.1 to 15.0% grafted (Sl); And

3 to 10 parts by weight of a metal salt and 0.1 to 1.0 part by weight of an antioxidant are added to 100 parts by weight of a substrate composed of 60 to 90% by weight of a carboxylic acid graft ethylene-propylene rubber and 10 to 40% by weight of a polyamide resin, (S2) mixing the mixture at a temperature of 150 to 200 DEG C at a rate of 30 to 90 rpm for 3 to 20 minutes using a Banbury mixer or a kneader .

The specific compositional ratios and the like of the rubber base material and various additives used in the present invention have already been described above and therefore will not be described here.

On the other hand, when the extrusion condition is less than the above range, the initiation reaction of the peroxide is not activated and the graft reaction rate is lowered and the graft rate tends to be lowered to 0.1% or less. If the extrusion condition is out of the above range, And unsaturated carboxylic acid are deteriorated and gelled.

If the mixing condition is less than the above range in step S2, ionization of the metal salt is not well-reacted, so that formation of intermolecular ion clusters is difficult and physical properties are lowered. If the mixing condition is over the range, There is a problem that a phenomenon of deterioration or gelation occurs.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples.

1. Preparation of Thermo-reversible Elastomer Composition

(Example 1)

0.15 parts by weight of an unsaturated carboxylic acid, 0.01 parts by weight of peroxide and 0.01 parts by weight of an antioxidant were mixed with 100 parts by weight of an ethylene-propylene rubber, followed by reaction extrusion at 180 ° C at an extrusion speed of 100 rpm to obtain a carboxylic acid graft ethylene- Propylene rubber was prepared and 100 parts by weight of a base composed of 60% by weight of the carboxylic acid graft ethylene-propylene rubber (CCA-g-EPDM) and 40% by weight of a polyamide resin (polyamide 6) , 3 parts by weight of a fatty acid metal salt and 0.5 part by weight of an antioxidant were mixed and dispersed at 180 캜 for 10 minutes using a kneader to prepare a supramolecular thermoplastic elastomer composition.

(Example 2)

0.15 parts by weight of an unsaturated carboxylic acid, 0.01 parts by weight of peroxide and 0.01 parts by weight of an antioxidant were mixed with 100 parts by weight of an ethylene-propylene rubber, followed by reaction extrusion at 180 ° C at an extrusion speed of 100 rpm to obtain a carboxylic acid graft ethylene- Propylene rubber was prepared and 100 parts by weight of a base composed of 60% by weight of the carboxylic acid graft ethylene-propylene rubber (CCA-g-EPDM) and 40% by weight of a polyamide resin (polyamide 6) , 3 parts by weight of fatty acid metal salt and 0.5 part by weight of an antioxidant were mixed and dispersed at 180 캜 for 10 minutes using a kneader to prepare a supramolecular thermoplastic elastomer composition.

(Example 3)

To 100 parts by weight of an ethylene-propylene rubber, 25.0 parts by weight of an unsaturated carboxylic acid, 0.3 parts by weight and 0.01 part by weight of a peroxide and an antioxidant, respectively, were mixed and reactively extruded at 180 DEG C at an extrusion rate of 150 rpm to obtain a carboxylic acid glass having a grafting rate of 15.0% Based on 100 parts by weight of a base composed of 70% by weight of the carboxylic acid graft ethylene-propylene rubber (CCA-g-EPDM) and 30% by weight of a polyamide resin (polyamide 6) 3.5 parts by weight of an organic metal salt, 3.5 parts by weight of a fatty acid metal salt and 0.5 part by weight of an antioxidant were mixed and dispersed at 180 ° C for 10 minutes using a kneader to prepare a thermally reversible elastomer composition.

(Example 4)

To 100 parts by weight of an ethylene-propylene rubber, 25.0 parts by weight of an unsaturated carboxylic acid, 0.3 parts by weight and 0.01 part by weight of a peroxide and an antioxidant, respectively, were mixed and reactively extruded at 180 DEG C at an extrusion rate of 150 rpm to obtain a carboxylic acid glass having a grafting rate of 15.0% Based on 100 parts by weight of a base composed of 80% by weight of the carboxylic acid graft ethylene-propylene rubber (CCA-g-EPDM) and 20% by weight of a polyamide resin (polyamide 6) 4 parts by weight of an organic metal salt, 4 parts by weight of a fatty acid metal salt, and 0.5 part by weight of an antioxidant were mixed and dispersed at 180 ° C for 10 minutes using a kneader to prepare a supramolecular thermoplastic elastomer composition.

(Example 5)

To 100 parts by weight of an ethylene-propylene rubber, 25.0 parts by weight of an unsaturated carboxylic acid, 0.3 parts by weight and 0.01 part by weight of a peroxide and an antioxidant, respectively, were mixed and reactively extruded at 180 DEG C at an extrusion rate of 150 rpm to obtain a carboxylic acid glass having a grafting rate of 15.0% Based on 100 parts by weight of a base composed of 90% by weight of the carboxylic acid graft ethylene-propylene rubber (CCA-g-EPDM) and 10% by weight of a polyamide resin (polyamide 6) 4.5 parts by weight of an organic metal salt, 4.5 parts by weight of a fatty acid metal salt and 0.5 parts by weight of an antioxidant were mixed and dispersed at 180 ° C for 10 minutes using a kneader to prepare a thermally reversible elastomer composition.

(Comparative Example 1)

5.0 parts by weight of a fatty acid metal salt and 0.5 part by weight of an antioxidant were mixed with 100 parts by weight of ethylene-propylene rubber (EPDM) and dispersed at 180 캜 for 10 minutes using a kneader to prepare a thermo-reversible elastomer composition.

(Comparative Example 2)

5.0 parts by weight of zinc oxide, 1.0 part by weight of stearic acid, 0.5 parts by weight of antioxidant, 1.0 part by weight of sulfur and 2.5 parts by weight of a vulcanization accelerator were mixed and dispersed in 100 parts by weight of ethylene-propylene rubber (EPDM) To prepare an elastomer composition.

(Comparative Example 3)

To 100 parts by weight of an ethylene-propylene rubber, 25.0 parts by weight of an unsaturated carboxylic acid, 0.3 parts by weight and 0.01 part by weight of a peroxide and an antioxidant, respectively, were mixed and reactively extruded at 180 DEG C at an extrusion rate of 150 rpm to obtain a carboxylic acid glass having a grafting rate of 15.0% 5.0 parts by weight of an organic metal salt, 5.0 parts by weight of a fatty acid metal salt and 0.5 part by weight of an antioxidant were mixed with 100 parts by weight of the carboxylic acid graft ethylene-propylene rubber (CCA-g-EPDM) And dispersed at 180 캜 for 10 minutes using a kneader to prepare a supramolecular thermoreversible rubber composition.

(Comparative Example 4)

0.5 part by weight of an antioxidant was added to 100 parts by weight of polyamide 6 and dispersed at 220 캜 for 10 minutes using a kneader to prepare a hypermolecular thermoreversible rubber composition.

(Comparative Example 5)

0.5 parts by weight of an antioxidant was mixed with 100 parts by weight of L2K70N (TPV) as a thermoplastic vulcanized rubber, and the mixture was dispersed at 180 DEG C for 10 minutes using a kneader to prepare an elastic composition.

2. Evaluation of thermoreversible elastomer composition

The elastic compositions prepared according to Examples 1 to 5 and Comparative Examples 1 to 5 were subjected to a characteristic test in the following manner to evaluate the mechanical properties of the composition and the results are shown in Table 1 below.

1) Specific gravity: The gravity was measured five times using an automatic gravity measuring device and the average was taken.

2) Hardness: The hardness was measured on the surface of a test piece with an Asker A type hardness meter according to ASTM D-2240.

3) Tensile strength: The test specimens were cut to a thickness of about 3 mm, cut into two pieces according to KS M6518, and tensile strength and elongation were measured according to KS M6518. At this time, three test pieces were used in the same test.

4) Tear strength: The tearing test was carried out according to KS M6518, and the measuring speed was measured five times at a speed of 100 m / min.

5) Recycling characteristics by repetitive machining: The initial test specimens manufactured through reactive extrusion and kneading are reworked with a kneader at 150 ° C for 5 to 10 minutes, and the tensile strength of the test specimen when reworked 2 to 5 times And the rate of decrease in physical properties was measured.

6) Permanent compressive strain: The tensile test was carried out in accordance with KS M6518, and the measurement conditions were 25% compression at 70 ° C for 22 hours and 160 ° C for 24 hours, and the permanent compressive strain was measured under these conditions.

7) Heat resistance: The heat resistance test was carried out according to KS M ISO 188, and the change in tensile strength and elongation was measured after heat treatment at 120 ° C for 72 hours.

8) Fluid resistance: The fluid resistance such as oil resistance and chemical resistance was measured according to ASTM D3182 and KS M ISO 461-2. The measurement of the oil resistance was carried out under the conditions of room temperature, 24 hours and 120 ° C and 72 hours in an ASTM # 3 oil atmosphere. Chemical resistance was measured by immersing in 1,1,1-trichloroethane solvent atmosphere at room temperature for 24 hours.

division Example Comparative Example One 2 3 4 5 One 2 3 4 5 Hardness (A-type) 95 96 91 84 77 45-46 54-55 60-61 80-81 75-76 importance 0.98 0.98 0.97 0.96 0.95 0.89 0.89 0.89 0.97 1.53 The tensile strength
(kgf / cm ² )
245
255
195
83
72
18
52
150
830
50 100% modulus
(kgf / cm ² )
175
180
173
61
65
6
13
22
-
15 300% modulus
(kgf / cm ² )
-




7
25
45
-
42 Elongation
(%)
220
230
220
245
265
1335
660
870
95
450 Phosphorus strength
(kgf / cm)
54
56
62
65
67
16
27
30
98
25 Reuse Characteristics
(%) Episode 2 10 9 9 10 11 30 * 10 11 15 3rd time 15 13 14 15 16 40 * 15 13 20 4 times 19 15 15 17 18 50 * 17 15 23 5 times 20 17 18 20 22 55 * 18 17 30 Permanent compression
Strain (%) ^{1 )}
56
59
50
48
47
98
30
59
12
66 Permanent compression
Strain (%) ^{2 )}
74
71
68
63
62
99
35
74
23
76 The tensile strength
Rate of change (%)
-4
-3
-14
-15
-15
-15
-10
-10
-2
-30 Elongation Change Rate (%)
+10
+10
-10
-10
-12
-15
10
+10
-5
-30 Weight change rate (%) ^{3 )}
17
16
20
23
24
20
15
20
32
12 Weight change rate (%) ^{4 )}
120
115
125
138
140
150
110
140
190
68 Weight change rate (%) ^{5 )}
-11
-10
-14
-17
-18
-25
-12
-15
-14
-24
* Not reworkable
1) 25% compression at 70 < 0 > C for 22 hours
2) 25% compression at 160 < 0 > C for 24 hours
3) Weight change after immersion at room temperature for 24 hours
4) Weight change after immersion at 120 ° C for 72 hours
5) Weight change after immersion in 1,1,1-trichloroethane solvent atmosphere at room temperature for 24 hours

As shown in Table 1, in Examples 1 to 5 according to the present invention, in consideration of Comparative Examples 1 to 5, not only physical properties such as mechanical strength and permanent compression toughness but also excellent heat resistance and chemical resistance were improved It can be seen that continuous processing and production are possible.

Although the amide-based supramolecular thermally reversible crosslinkable elastomer composition having excellent heat resistance, chemical resistance, mechanical strength and permanent compression strain according to the preferred embodiment of the present invention has been described above with reference to the above description and drawings, It will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit of the invention.

Claims (3)

In the supramolecular thermoplastic reversible crosslinkable elastomer composition,
3 to 10 parts by weight of a metal salt and 0.1 to 1.0 part by weight of an antioxidant are added to 100 parts by weight of a substrate composed of 60 to 90% by weight of a carboxylic acid graft ethylene-propylene rubber and 10 to 40% by weight of a polyamide resin ,
The carboxylic acid grafted ethylene-propylene rubber is obtained by adding 0.15 to 25 parts by weight of an unsaturated carboxylic acid, 0.01 to 0.3 part by weight of peroxide and 0.01 to 1.0 part by weight of an antioxidant to 100 parts by weight of an ethylene- And an acid is grafted in an amount of 0.1 to 15.0%. The amide-based supramolecular thermally reversible crosslinkable elastomer composition is excellent in heat resistance, chemical resistance, mechanical strength and permanent compression strain. delete delete

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