KR101735654B1

KR101735654B1 - Self healing elastomeric nanocomposite, its crosslinked product, and kit thereof

Info

Publication number: KR101735654B1
Application number: KR1020150140264A
Authority: KR
Inventors: 안대업; 이대학; 김성진
Original assignee: 넥쌍
Priority date: 2015-10-06
Filing date: 2015-10-06
Publication date: 2017-05-15
Also published as: KR20170040950A

Abstract

The present invention relates to a self-healing elastomer nanocomposite comprising a polymeric elastomer, an amphiphilic fatty acid derivative and a nanofiller, a crosslinked body thereof, and a kit comprising the same, wherein the complex, the crosslinked body and the kit according to the present invention have excellent self- And can be widely applied to various industrial fields.

Description

SELF HEALING ELASTOMERIC NANOCOMPOSITE, ITS CROSS LINKED PRODUCT, AND KIT THEREOF FIELD OF THE INVENTION [0001] The present invention relates to a self-healing elastomeric nanocomposite,

The present invention relates to a self-healing elastomeric nanocomposite, a crosslinked body thereof, and a kit comprising the same.

Self-healing polymeric materials can be produced by a variety of methods with polymeric materials that self-heal fractures or cuts generated by external physical damage.

Polymer materials in which polymerization is initiated by external stimuli such as light, heat, or moisture are added as a kind of self-healing inducer, can heal damaged areas by polymerizing monomers exposed to external stimuli in the event of damage. However, such monomer-polymerized self-healing polymers require external stimuli such as light, heat, or moisture for self-healing, and they form irreversible covalent bonds during self-healing, thereby causing another damage to the self- In this case, there is a disadvantage that it is not possible to raise the stock price. In addition, for the production of polymer products, it is necessary to carry out processes such as mixing, processing, molding or crosslinking at a high temperature and a high pressure. Since the monomers are difficult to stably exist in the polymer matrix during the process, It is difficult to apply directly.

In addition, a monomer-polymerized self-healing polymer prepared by adding an unreacted monomer protected with microcapsules to a polymer material containing a polymerization initiator has a problem in that the monomer released from the capsule simultaneously with the damage is dispersed in the polymer matrix The polymerization initiator is polymerized by the polymerization initiator so that the damaged site can be cured by itself. The healing of the polymer can be initiated without any external stimulation, but it is impossible to re-damage the already healed area, and it is impossible to apply directly to the polymer raw material before processing due to the fragile microphone capsule. There are disadvantages.

Self-healing polymers can also be prepared by generating reversible physical bonds, such as hydrogen or ionic bonds, to the damaged site. Oligomers or polymers prepared so as to form strong hydrogen or ionic bonds between molecules can be reversibly supramolecularly assembled at the damaged sites and can be used as self-healing polymers. Since the supercritical self-healing polymer is initiated and progressed without any external stimulus unlike the above-mentioned monomer-polymerized self-healing polymer, the damaged region is healed by reversible supramolecular assembly, It is possible to produce a self-healing polymer product through general polymer blending, processing and molding process.

However, such a supramolecular self-healing polymer is still expensive for commercial application, and the supramolecular-assembled polymer having high self-healing capability has a disadvantage in that initial mechanical properties are too low for commercial use. Therefore, it is necessary to develop a nanocomposite having a self-healing function and a commercially available physical property.

US 2006193569 (published August 31, 2006)

It is an object of the present invention to provide a nanocomposite excellent in self-healing performance, a crosslinked body thereof, and a kit containing the same.

In order to achieve the above object, the present invention provides a self-healing elastomer nanocomposite comprising:

(i) a polymeric elastomer;

(ii) an amphiphilic fatty acid derivative; And

(iii) Nanofiller.

The polymeric elastomer may be an ethylene-vinyl acetate copolymer, but is not limited thereto.

The amphiphilic fatty acid derivative may be selected from the group consisting of an amphiphilic carboxylic acid-based compound, an amphiphilic amine-based compound, a fatty acid ester compound, and mixtures thereof.

The amphiphilic carboxylic acid compound may be any one selected from the group consisting of a saturated or unsaturated fatty acid, a double carboxylic acid, a carboxylic acid metal salt, a carboxylic acid or a maleic anhydride substituted polymer, or a combination thereof.

The amphiphilic amine compound may be any one selected from the group consisting of fatty acid amines, double amines or amides, amine or amide metal salts, and combinations thereof.

The fatty acid ester may be selected from castor oil, coconut oil, olive oil, palm oil, soybean oil, dioctyl sebacate, dibutyl sebacate, dioctyl adipate, dioctyl phthalate, di- Dibutyl phthalate, adipic acid polyester, and combinations thereof.

The nanofiller is a nanoparticle having a specific axis length of 100 nm or less, which is selected from inorganic nanoparticles, organic nanoparticles, chemically modified nanoparticles thereof, and combinations thereof. Lt; / RTI > Wherein the nanoparticles are selected from the group consisting of carbon black, nano-clay, nanosilica, polyheadal oligomeric silsesquioxane (POSS), lyered double hydroxide, calcium nano-carbonate, carbon nanotubes, Particles, and combinations thereof.

In one embodiment, the content of the nanofiller may be 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the elastomeric polymer.

In one embodiment, the amount of the amphiphilic fatty acid derivative of the nanocomposite may be 5 to 50 parts by weight based on 100 parts by weight of the elastomeric polymer, and the content of the nanofiller may be 0.1 to 20 parts by weight.

The nanocomposite may further include any one selected from an inorganic additive, an organic additive, and a mixture thereof. In one embodiment, the nanocomposite may be contained in an amount of 50 parts by weight or less based on 100 parts by weight of the elastomeric polymer.

In addition, the nanocomposite may further include a crosslinking agent. In one embodiment, the nanocomposite may include 0.1 to 10 parts by weight based on 100 parts by weight of the elastomeric polymer.

Also, the present invention provides a crosslinked product prepared by crosslinking the nanocomposite.

Also, the present invention provides a rubber regeneration kit comprising the nanocomposite or the crosslinked body.

The self-healing elastomeric nanocomposite according to the present invention, the crosslinked body thereof and the kit comprising the same can self-heal the fracture or cut surface generated by external physical damage, and restore the initial mechanical performance of the material after self-healing And can be widely applied to various industrial fields.

FIG. 1 shows an embodiment of an evaluation method for evaluating the natural healing performance of the nanocomposite according to the present invention.

Hereinafter, the present invention will be described in detail.

According to one embodiment of the present invention there is provided a self-healing elastomer nanocomposite comprising:

(i) a polymeric elastomer;

(ii) an amphiphilic fatty acid derivative; And

(iii) Nanofiller.

Polymer elastomer

The elastomeric polymer used in the present invention has a glass transition temperature lower than room temperature, a melting temperature and a crystallinity lower than that of a general crystalline thermoplastic polymer such as polyethylene and polypropylene, plateau region and exhibits elasticity, and may preferably include one or more of a single polymer elastomer, a random copolymer type polymer elastomer, and a block copolymer polymer elastomer as described below.

(1) a single polymer elastomer

In one embodiment, the single polymeric elastomer may be natural rubber, polybutadiene, epichlorohydrin polymer, polychloroprene, or silicone rubber.

(2) Random copolymer type polymer elastomer

In one embodiment, the random copolymer type polymeric elastomer includes a nitrile rubber; Styrene-butadiene rubber; Epichlorohydrin-ethylene oxide copolymer; Ethylene-vinyl acetate copolymers; Ethylene-polyethylene; Chlorosulfonated polyethylene; Polyurethane rubber; It is also possible to use two or more different chemical components or structures of different vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, tetrafluoroethylene, perfluoro (methyl vinyl ether flurocarbon rubber prepared by polymerizing a fluorocarbon monomer such as perfluoro (methyl vinyl ether) or the like; A fluorocarbon rubber prepared by polymerizing two or more fluorocarbon monomers and at least one non-fluorine monomer such as propylene, a monomer having a crosslinking reactor such as isobutylene monomer and a small amount of isoprene is polymerized Butyl rubber; Or a polyacrylic rubber prepared by polymerizing monomers having at least one acrylic ester monomer and a small amount of a crosslinking reactor.

(3) Block copolymer type polymer elastomer

In one embodiment, the elastomeric polymer wherein the block copolymer body are poly (styrene - b - isoprene) diblock copolymer {poly (styrene- b -isoprene) diblock copolymer}, poly (styrene - b - butadiene) diblock copolymer {poly (styrene- b -butadiene) diblock copolymer} , poly (styrene - b - isoprene - b - styrene) triblock copolymer {poly (styrene- b -isoprene- b -styrene ) triblock copolymer}, poly (styrene - b - butadiene - b - styrene) triblock copolymer {poly (styrene- b -butadiene- b -styrene ) (SBS) triblock copolymer}, poly (styrene - b - ethylene / butylene - b - styrene) triblock copolymer { poly (styrene- b -ethylene / butylene- b -styrene) triblock copolymer} or poly (styrene - b - ethylene / propylene - b - styrene) triblock copolymer {poly (styrene- b -ethylene / propylene- b -styrene ) triblock copolymer}.

In one embodiment of the present invention, the polymer elastomer may be an ethylene-vinyl acetate copolymer (EVA). The EVA has a relatively low glass transition temperature ( T _g ) and crystallinity, It is easy to physically mix with a fatty acid derivative and a nanofiller and can be crosslinked with a commercial peroxide cross-linking agent.

As described later, the present inventors have found that in one embodiment EVA EVA 28 (Arkema, Evatane 28-05), EVA45 (Du Pont- Mitsui Polychemicals Co., Evaflex 45LX), and EVA70 (Lanxess, Levapren 700HV). EVA is a polymer elastomer whose polarity and crystallinity vary according to the content of VA. EVA28 is a polymer material having a relatively low polarity and high crystallinity, whereas EVA70 is a polymer material having a relatively high polarity and a low crystallinity. Therefore, it is believed that the nanocomposite provided by the present invention can be easily applied to many other polymeric elastomer materials having various polarities and crystallizabilities.

Amphibian Fatty acid derivative

The amphiphilic fatty acid derivative according to the present invention is preferably an amphiphilic fatty acid or derivative thereof having a hydrophobic group and a hydrophobic group at the same time. In one embodiment, the amphiphilic fatty acid derivative is an amphiphilic carboxylic acid compound, an amphiphilic amine compound, Esters, and mixtures thereof.

In one preferred embodiment, the amphiphilic carboxylic acid compound according to the present invention is selected from the group consisting of palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, But are not limited to, the same saturated and unsaturated fatty acids, hexadecanedioic acid, tetradecanedioic acid, undodecanedicarboxylic acid, dodecanedioic acid (DDA) A metal salt of carboxylic acid such as zinc stearate (ZS), zinc acetate (ZA), magnesium stearate, calcium stearate and the like, a polymer substituted with carboxylic acid or maleic anhydride, and a combination thereof Lt; / RTI >

In one preferred embodiment, the amphiphilic amine compound is selected from the group consisting of stearyl amine, SAmine, stearamide, SAmide, ethylene-bis-stearamide, erucamide, Fatty amines or amides derived from fatty acids such as oleamide, behenamide and the like, and diamines such as 1,12-diaminododecane (DAD), adipamide Or an amide, or an amine or amide metal salt derived therefrom. The amphiphilic amine compound may be used alone or in combination of two or more.

In another preferred embodiment, the fatty acid ester compound is selected from the group consisting of oil extracted from plants and animals such as caster oil (CSO), coconut oil (CCO), olive oil (OLO), palm oil (PO) Ester compounds containing at least four aliphatic carbon atoms such as octyl sebacate, dibutyl sebacate, dioctyl adipate, dioctyl phthalate, di- n -hexyl phthalate, diamyl phthalate, dibutyl phthalate and adipic acid polyester, Lt; / RTI >

In a preferred embodiment, the amount of the amphiphilic fatty acid derivative may be 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the polymeric elastomer.

Nanofiller

The nanofiller according to the present invention is a nanoparticle having a length of a specific axis of a primary particle of nanoscale, preferably 100 nm or less. The nanoparticle is an organic nanoparticle, an inorganic nanoparticle, a chemically modified nanoparticle thereof, Lt; / RTI > In one preferred embodiment, the nanoparticles are selected from the group consisting of carbon black, nano-clay, nanosilica, polyhedral oligomeric silsesquioxane (POSS), lyered double hydroxide, Tubes, graphens, colloidal nanoparticles, or mixtures thereof. In addition, commercially available nanofillers such as the following may be used as an embodiment, but the present invention is not limited thereto.

(1 ) Organic nano-clay in which inorganic cations located between layers of natural nano-clay are replaced with amphiphilic cations of two different polarities : ammonium, ammonium, substituted with dimethyl or dihydrogenated tallow groups Modified organic nanoclay (Dellite 67G, Laviosa Chemica Mineraria SpA); (Cloisite 30B, Southern Clay Products Inc.) modified with an ammonium salt substituted with methyl, tallow and bis-2-hydroxyethyl groups.

(2) Two kinds of POSS substituted with different organic functional groups : glycidyl POSS cage mixer (EP0409, Hybrid Plastics) in which eight propyl glycidyl ether groups are substituted for eight silicon molecules Inc.); AminopropylIsooctyl POSS (AM0270, Hybrid Plastics Inc.) substituted with one - (CH ₂ ) ₃ -NH ₂ and seven isooctyl groups in eight silicon molecules.

(3) Hydrophilic fumed nanosilica (Aerosil 200, Evonic Industries, average primary particle size = 12 nm), which is not chemically modified .

(4) Chemically modified hydrophilic nano-calcium carbonate (CACO-N50 technology, particle size <50 nm).

(5) Multi-walled carbon nanotubes (CM250, Hanwha Chemical Co., diameter = 10 to 15 nm, length = 100 μm ).

In one preferred embodiment, the content of the nanofiller may be 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the elastomeric polymer.

In one particularly preferred embodiment, the content of the nanofiller may be 0.1 to 5 parts by weight, more preferably 3 parts by weight, based on 100 parts by weight of the elastomeric polymer.

When the nanofiller is ideally dispersed in the polymer material, it can effectively improve the thermal stability, barrier properties, and flame retardancy as well as the mechanical properties of the polymer material. These nanofillers have a relatively large surface area that can interact with polymeric materials per unit volume as compared to conventional microfillers. Therefore, it is possible to achieve the same level of performance improvement as that of the micro-filler even in a relatively small amount. In addition, this makes it possible to produce high performance polymer nanocomposites in which the inherent advantages of polymeric materials, such as excellent melt processability, flexibility, elasticity and light weight, are maximally maintained or improved.

Therefore, in the present invention, by adding a small amount of nanofiller to a supramolecular self-healing polymer elastomer having a high self-healing ability including a fatty acid derivative but having a low initial mechanical property and being greatly limited in commercial use, And a crosslinked body of the nanocomposite having improved initial mechanical strength.

Further, the nanofiller according to the present invention contains an amphiphilic fatty acid derivative having a polar group and is added to a supramolecular self-healing polymer elastomer having excellent self-healing performance at a relatively low temperature of 80 ° C or less, Elastic nanocomposites having mechanical strength and self-healing ability and crosslinked bodies thereof can be produced.

additive

According to one embodiment, the nanocomposite according to the present invention may optionally further comprise organic and / or inorganic additives. The inorganic additive includes metal and ceramic inorganic additives such as carbon black, calcium carbonate (CaCO ₃ ), talc, china clay, graphite, silica, mica, antimony trioxide, lead oxide, aluminum hydroxide, magnesium hydroxide, magnesium oxide, And the like. However, the present invention is not limited thereto. The organic additive may include, but is not limited to, an antioxidant, a compatibilizer, a stabilizer, a plasticizer, a softener, an extender, a pigment, a coupling agent, a flame retardant, a crosslinking agent, Preferably, the organic additive and / or the inorganic additive may be contained in an amount of 50 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the elastomeric polymer.

Manufacture of Self-Healing Elastomer Nanocomposites

The nanocomposite according to the present invention can be produced by mixing a polymeric elastomer, an amphiphilic fatty acid derivative and a nanoparticulate polymer by using various mixers such as an internal mixer and an open mixer at a temperature higher than the glass transition temperature or the melting temperature of the polymeric elastomer Or a reactive mixing method in which a chemical reaction takes place between the components during the melt-mixing. In an embodiment, the closed mixer may be a Banbury mixer, a kneader mixer, or an extruder, and the open mixer may be a roll-mill, but is not limited thereto .

Self-healing elastomer nanocomposite Crosslinked body

The present invention provides a crosslinked body of a nanocomposite wherein a polymeric elastomer is chemically or physically crosslinked. The chemical crosslinking refers to a case where crosslinking is formed by an intermolecular chemical reaction. In this case, a crosslinking agent may be additionally contained in the mixture of the polymeric elastomer, the amphiphilic fatty acid derivative and the nanofiller, and the crosslinking agent may be added in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the elastomeric polymer. The physical crosslinking refers to the case where crosslinking is reversibly formed by secondary bonding or phase separation generated by intermolecular ionic bonding, hydrogen bonding, dipole-dipole interaction, van der Waals interaction, or the like , The physically crosslinked elastomer nanocomposite does not include a crosslinking agent.

Rubber regeneration Kit

Further, the present invention provides a rubber regeneration kit. The rubber regeneration kit may include a nanocomposite comprising the polymeric elastomer and the amphiphilic fatty acid derivative according to the present invention as a rubber regeneration material. In one preferred embodiment, the rubber regeneration kit may include a nanocomposite, which additionally comprises a nanofiller, as a rubber recycling material. The rubber recycling material included in the rubber kit according to the present invention can be filled or applied to the damaged area of the rubber material to restore the performance of the material.

In one embodiment, the kit of the present invention may comprise a non-crosslinked nanocomposite or a crosslinked body thereof. When the non-crosslinked nanocomposite is included in the kit, the viscosity of the nanocomposite is relatively low, and the damage site of the rubber material can be easily filled with the hand, which is excellent in workability. On the other hand, when the crosslinked nanocomposite is included in the kit, the damaged site can be regenerated at a relatively low temperature.

The kit according to the present invention may also include a heating band or tape for heating (a healing band or tape), a temperature control device, or a tape for fixing a heat application site.

Hereinafter, the present invention will be described in detail with reference to examples. The following embodiments are merely illustrative examples to enable those skilled in the art to understand the present invention in more detail, and the scope of the present invention is not limited by the embodiments. In addition, those skilled in the art will be able to apply various modifications within the meaning of the present invention, thereby obtaining and confirming the effect to be achieved by the present invention.

Self-healing elastomer Nanocomposites and their implications Bridged Produce

As a representative example of the process of producing the nanocomposite and the crosslinked product thereof, a nanocomposite having a composition ratio and composition ratios of Example 10 shown in Table 2 below and a crosslinked product thereof were prepared.

First, the present inventors masticated ethylene vinyl acetate copolymer 45 (EVA45, manufactured by Du Pont-Mitsui Polychemicals Co., Ltd., product name: Evaflex 45LX) having a vinyl acetate content of 45 wt% at 80 ° C for 10 minutes using a double roll mill .

The following components are then added:

Amphipathic fatty acid derivative: Castor oil (product name: CSO)

Nano-filler: Organic nano-clay (Cloisite 30B, product of Southern Clay Products Inc.)

Crosslinking agent: bis ( t -butylperoxyisopropyl) benzene (PBP-98, NOF Corporation, Perbutyl P), and

Antioxidant Rhenogran® PCD-50 / EVA (RheinChemie)

Were further mixed at 80 DEG C for 10 minutes using a double roll mill at a mixing ratio shown in Table 1 to obtain a nanocomposite. The prepared nanocomposite was compressed at 170 캜 to 12.5 MPa and crosslinked for 15 minutes to prepare a 2 mm thick, plate-like cross-linked body.

Component (trade name) Compounding ratio (Phr *) Polymer elastomer EVA45 100 Amphiphilic fatty acid derivative CSO 20 Nanofiller Cloisite 30B 3 Cross-linking agent Bis ( t -butylperoxyisopropyl) benzene (PBP-98) 2 Antioxidant Rhenogran® PCD-50 / EVA
(Mixture of polycarbodiimide, EVA and dispersant) 3

In the above Table 1, phr is an abbreviation of parts per hundred parts of the elastomeric polymer. In Table 1 above, only one polymeric elastomer, EVA 45, is included in the composition.

Self-healing elastomer Bridged Mechanical How to evaluate performance

The mechanical performance of the crosslinked body such as tensile strength (TS) and elongation at break (EB) was measured using a universal tensile tester in accordance with DIN 53504.S2, 1-1 standards. The higher the tensile strength and the elongation at break, the better the overall mechanical performance.

Evaluation method for self-healing efficiency

The natural healing performance was determined by cutting the dumbbell specimens into two pieces and measuring the ratio of the mechanical properties recovered after self-healing and the mechanical properties before cutting for a given temperature and time. In other words, expressed by dividing the self-healing performance of the tensile strength (TS ₀₎ or elongation at break of the initial sample prior to cutting the tensile strength (TS) or elongation at break (EB) measurements after self-healing embodiment (EB ₀₎ in the present invention respectively, . Specifically, the cut surfaces of the rubber cross-linked body specimens completely cut into two pieces were cured at a predetermined temperature for 24 hours while the cut surfaces of the cut specimens were brought into contact with each other as illustrated in FIG. 1, and the recovered mechanical properties were measured by a universal tensile tester .

Self-healing elastomer Nanocomposites and their implications The crosslinked body Using the measured performance

According to the above-mentioned representative preparation example, nanocomposites and their crosslinked bodies were prepared using the components and the blending ratios shown in Table 2 below. All the nanocomposites described in Table 2 included a crosslinking agent (PBP-98, 2 phr) and antioxidants (Rhenogran PCD-50, 3Phr) in addition to the components listed in Table 2 below. What the abbreviations given in Table 2 mean is described herein before.

The thus-obtained nanocomposite and its crosslinked material were measured for mechanical performance and the like according to the measurement method described above, and the results are shown in Table 2 below.

The example numbers marked " * " represent Comparative Examples which do not include the nanofiller according to the present invention.

Example ingredient Composition ratio (Phr) Self-Healing Temperature (℃) TS / TS ₀ (MPa) EB / EB ₀ (%) One* EVA28
ZS
CSO 100
10
30 80
11/17
680/1000 2 The components of Example 1 *
AM0270 140
One 80 9.3 / 20 570/1100 3 The components of Example 1 *
Aerosil 200 140
3 80 5.6 / 20 580/940 4 The components of Example 1 *
CACO-N50 140
3 80 10/20 710/1000 5 * EVA45
ZS
CSO 100
10
20 80

40 TS ₀ = 6.9
Specimen breaks at other than the cut part.
0.9 / 6.9 EB ₀ = 970

430/970 6 Example 5 * Component +
EP0409 130
One 80
40 5.6 / 10.2
1.3 / 10.2 910/1100
610/1100 7 Example 5 * Component +
Cloisite 30B 130
3 80
40 5.7 / 9.6
1.3 / 9.6 920/1100
600/1100 8 Example 5 * Component +
Aerosol 200 130
3 80
40 6.2 / 9.9
1.6 / 9.9 980/1100
670/1100 9 Example 5 * Component +
CACO-N50 130
3 80
40 5.6 / 10.5
1.2 / 10.5 950.1200
560/1200 10 EVA45
CSO
Cloisite 30B 100
20
3 80 TS ₀ = 10.4
Specimen breaks at other than the cut part. EB ₀ = 890 11 EVA45
CSO
Dellite 67G 100
20
One 60 1.6 / 3.4 400/760 12 EVA45
CSO
Dellite 67G 100
20
3 60 1.2 / 9.1 300/830 13 EVA45
CSO
Dellite 67G 100
20
10 60 0.8 / 9.6 130/960 14 * EVA70
ZS
CSO 100
10
10 80
40 TS ₀ = 1.3
Specimen breaks at other than the cut part. EB _O = 650 15 Example 14 * Component of +
AM0270 120
One 40 1.6 / 2.2 670/850 16 Example 14 * Component of +
Dellite 67G 120
3 80
40 TS ₀ = 2.0
Specimen breaks at other than the cut part. EB _O = 750 17 Example 14 * Component of +
CACO-N50 120
3 40 1.9 / 3.2 680/960 18 Example 14 * Component of +
CM250 120
3 80
40 TS ₀ = 3.1
Specimen breaks at other than the cut part. EB _O = 600 19 EVA70
CSO
Cloisite 30B 120
10
3 80
40 1.4 / 2.7
0.82 / 2.7 310/660
310/660

In Examples 1 *, 2-4, 10-13, 15 and 17, performance measurement experiments were performed at one temperature such as 40 ° C, 60 ° C or 80 ° C.

In Examples 5 *, 6-9, 14 *, 16, 18 and 19, performance measurement experiments were carried out at 80 ° C and 40 ° C, respectively.

In Examples 14 *, 16 and 18, the experimental results are the same at 40 ° C and 80 ° C.

From the experimental results shown in Table 2, the following contents can be confirmed.

(1) The initial mechanical properties of the crosslinked material were observed to increase as the amount of the nanofiller added increased, as the amount of the fatty acid derivative decreased. On the other hand, the self - healing ability of the crosslinked body increased with increasing amount of fatty acid derivative and with increasing temperature of self - healing, as the amount of nanofiller decreased.

(2) However, the addition of a relatively small amount (for example, 3 phr or less) of the nanofiller significantly increases the initial mechanical properties without significantly decreasing the self-healing performance of each body.

Rubber regeneration In kit The included nanocomposites and their implants Crosslinked body Produce

As one example of the nanocomposite contained in the rubber regeneration kit and the crosslinked body thereof, the nanocomposite was prepared by mixing using the double roll mill at the mixing ratios mentioned in Table 2 above. The crosslinked product thereof was compressed to 12.5 MPa at 170 DEG C and crosslinked for 15 minutes to prepare a plate having a thickness of 2 mm.

Rubber regeneration Kit Rubber regeneration effect

The rubber regeneration kit according to the present invention confirmed the rubber regeneration effect by the following procedure. Step 1. A small excess of self-healing compound is manually pressed into the damaged portion of the cable. Step 2. The damaged portion was wound and fixed using a Teflon tape. Step 3. A heat tape was wound on the tape. Step 4. Connect the tape to a temperature controller for 2 hours at 150 ° C for the uncrosslinked nanocomposite and 24 hours at the lowest healing temperature of 40 ° C to 80 ° C for the crosslinked nanocomposite Respectively. Step 5. Remove the heating tape and trim the cable surface with a razor.

The rubber regeneration effect of the rubber regeneration kit was confirmed by measuring the tensile strength and elongation at break of the regenerated cable sheath.

After drilling a 5 mm diameter hole in the rubber sheath of the non-halogen fireproof cable (XLPO-6MR) of Nexans Kukdong, the existing recycled material (the same material as XLPO-6MR but not crosslinked) and the invention according to the invention And repair was carried out with the self-healing regenerative material provided by the present invention. Conventional recycled materials have a very high viscosity and can not be filled with the hand by pressing them. Therefore, the phosphorus was used and the temperature was maintained at 150 ° C for 2 hours for regeneration and crosslinking.

The tensile strength and elongation at break of the samples recovered with conventional recycled materials were 5.9 MPa and 110%, respectively, due to premature failure at the repair site. On the other hand, the tensile strength and the elongation at break of the self-healing elastomeric nanocomposite of Example 19 recovered and crosslinked at 150 ° C for 2 hours were 9.1 MPa and 210%, respectively, The tensile strength and elongation at break of the samples were 24.8 hours at 80 ℃ and 8.8 MPa and 190%, respectively.

Also, when the self-healing elastomer composite of Example 14 was used as a recycling material and regenerated and crosslinked at 150 DEG C for 2 hours, the tensile strength and the elongation at break were 8.2 MPa and 170%, respectively. Therefore, it can be seen that the rubber regenerating kit comprising the self-healing elastomeric nanocomposite or the crosslinked form thereof of the present invention as a regenerating material shows superior workability and regenerating effect as compared with the conventional rubber regenerating kit.

Claims

(i) a polymeric elastomer;
(ii) an amphiphilic fatty acid derivative; And
(iii) a nanofiller,
Wherein the content of the nanofiller is 0.1 to 20 parts by weight based on 100 parts by weight of the elastomeric polymer.

The method according to claim 1,
The amphiphilic fatty acid derivative is selected from the group consisting of an amphiphilic carboxylic acid-based compound, an amphiphilic amine-based compound, a fatty acid ester compound, and mixtures thereof.

The method according to claim 1,
Wherein the polymeric elastomer is an ethylene-vinyl acetate (EVA) copolymer.

3. The method of claim 2,
Wherein the amphiphilic carboxylic acid compound is any one selected from the group consisting of a saturated or unsaturated fatty acid, a double carboxylic acid, a carboxylic acid metal salt, a carboxylic acid or a maleic anhydride substituted polymer, and a combination thereof.

3. The method of claim 2,
Wherein the amphiphilic amine compound is any one selected from the group consisting of fatty acid amines, double amines or amides, amine or amide metal salts, and combinations thereof.

3. The method of claim 2,
The fatty acid ester may be selected from the group consisting of castor oil, coconut oil, olive oil, palm oil, soybean oil, dioctyl sebacate, dibutyl sebacate, dioctyl adipate, dioctyl phthalate, di-n-hexyl phthalate, diamyl phthalate Butyl phthalate, adipic acid polyester, and combinations thereof.

The method according to claim 1,
The nanofiller is a nanoparticle having a specific axis length of 100 nm or less, and is selected from the group consisting of organic nanoparticles, inorganic nanoparticles, chemically modified nanoparticles thereof, and combinations thereof. Complex.

8. The method of claim 7,
The nanoparticles may be selected from the group consisting of carbon black, nano clay, nanosilica, polyhedral oligomeric silsesquioxane (POSS), lyered double hydroxide, calcium nano-carbonate, carbon nanotubes, graphene, colloidal nanoparticles And a combination thereof.

The method according to claim 1,
Wherein the amount of the amphiphilic fatty acid derivative is 5 to 50 parts by weight based on 100 parts by weight of the elastomeric polymer, and the content of the nanofiller is 0.1 to 20 parts by weight.

The method according to claim 1,
And 50 parts by weight or less, based on 100 parts by weight of the polymeric elastomer, of an inorganic additive, an organic additive, and a mixture thereof.

The method according to claim 1,
Wherein the elastomer nanocomposite further comprises 0.1 to 10 parts by weight of a crosslinking agent based on 100 parts by weight of the elastomeric polymer.

A crosslinked body produced by crosslinking the nanocomposite of claim 1.

A rubber regeneration kit comprising the nanocomposite of claim 1 or the crosslinked form of claim 12.

A cable comprising a self-healing elastomeric nanocomposite, said nanocomposite comprising:
(i) a polymeric elastomer;
(ii) an amphiphilic fatty acid derivative; And
(iii) Nanofiller.

15. The method of claim 14,
Wherein the content of the nanofiller is 0.1 to 20 parts by weight based on 100 parts by weight of the polymeric elastomer.