WO2016080789A1 - Complexe organique nanoargile-polymère et son procédé de production - Google Patents

Complexe organique nanoargile-polymère et son procédé de production Download PDF

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WO2016080789A1
WO2016080789A1 PCT/KR2015/012489 KR2015012489W WO2016080789A1 WO 2016080789 A1 WO2016080789 A1 WO 2016080789A1 KR 2015012489 W KR2015012489 W KR 2015012489W WO 2016080789 A1 WO2016080789 A1 WO 2016080789A1
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nanoclay
organic
salt
polymer
polymer composite
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Korean (ko)
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최진호
양재훈
박대환
이지희
류현주
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이화여자대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/05—Forming flame retardant coatings or fire resistant coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the present application relates to an organic nanoclay-polymer composite and a method for preparing the organic nanoclay-polymer composite.
  • Polymer materials are widely used in various fields in modern society because of their high strength and light weight. However, polymer materials have a problem inherent in fire hazard because they are easily burned by fire. In order to solve this problem, many efforts have been made to flame retardant polymers.
  • a method for improving the flame retardancy of the polymer a method of dispersing the oligomer of the phosphorus flame retardant with the polymer (Korean Patent No. 1998-0002056), or encapsulating the flame retardant with a thermoplastic resin first, and then organophosphorus flame retardant in the polymer
  • a method of dispersing (Korean Patent Publication No. 2002-0027783) and the like have been proposed, but flame retardant properties are imparted only when the flame retardant is contained in an amount of 15 wt% or more, but it is difficult to prevent a decrease in mechanical properties due to an increase in the content of the flame retardant.
  • the present application is to provide an organic nanoclay-polymer composite and a method for preparing the organic nanoclay-polymer composite.
  • a first aspect of the present disclosure provides an organic nanoclay-polymer composite comprising an organic cationic nanoclay, an organic anionic nanoclay, and a polymer.
  • a second aspect of the present disclosure is directed to preparing a cationic surfactant-containing solution and an anionic surfactant-containing solution, respectively;
  • the cationic surfactant-containing solution was stirred with a cationic nanoclay-dispersed solution and the anionic surfactant-containing solution was stirred with anionic nanoclay-dispersed solution to form an organic cationic nanoclay and an organic anionic nanoclay.
  • a cationic surfactant is inserted between the layers of cationic nanoclays, and an anionic surfactant is inserted between the layers of anionic nanoclays to organicize two different nanoclays, and
  • the space of the cationic nanoclay dispersed during the combustion of the organic nanoclay-polymer composite is a small size of layered material anionic nanoclay It can effectively block the contact with air by filling it, making it easier to form char, thereby increasing thermal stability and mechanical properties simultaneously, and minimizing the use of foaming compounds for reducing flame retardant and calorific value. From this, the thermal stability and mechanical properties of the polymer can be maintained. .
  • 1 is a comparative schematic diagram of the flame retardant mechanism of the organic nanoclay-polymer composite and the polymer according to an embodiment of the present application.
  • 3A and 3B are results of measuring elastic modulus and tensile strength of an organic nanoclay-polymer composite and a polymer (EVA) according to an embodiment of the present application.
  • 5A and 5B are results of measuring elastic modulus and tensile strength of an organic nanoclay-polymer composite and a polymer (PP) according to an embodiment of the present application.
  • FIG. 6 is a heat release rate measurement result by the cone calorimeter test method of the organic nanoclay-polymer composite and the polymer (EVA) according to an embodiment of the present application.
  • step to or “step of” does not mean “step for.”
  • the term "combination (s) thereof" included in the representation of a makushi form refers to one or more mixtures or combinations selected from the group consisting of the components described in the representation of makushi form, It means to include one or more selected from the group consisting of the above components.
  • alkyl may be one containing a linear or branched, saturated or unsaturated C 1-10 alkyl group, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, It may be, but is not limited to, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or all possible isomers thereof.
  • a first aspect of the present disclosure provides an organic nanoclay-polymer composite comprising an organic cationic nanoclay, an organic anionic nanoclay, and a polymer.
  • the nanoclay or clay (cationic clay or anionic clay) is hydrophilic, and is a polymer (PP), poly (propylene), EVA (ethylene) which is widely used in exterior materials of construction, automobiles and home appliances
  • Polymers such as vinyl acetae copolymer (ABS) and acrylonitrile butadiene styrene copolymer (ABS) are hydrophobic, and in order to form the complex in which the nanoclay is dispersed in the polymer, that is, in the exfoliated state, the surface of the nanoclay is hydrophobic. It is necessary to modify, and accordingly, the nanoclay may be organicized using an organic agent, but may not be limited thereto.
  • the organic nanoclay-polymer composite may be one having a flame retardant or calorific value reducing effect, but may not be limited thereto.
  • the organic nanoclay-polymer complex may be to further include a foaming compound, but may not be limited thereto.
  • FIG. 1 shows a schematic diagram of (a) a polymer, (b) an organic cationic nanoclay-foaming compound-polymer complex, and (c) an organic nanoclay-foaming compound-polymer complex according to the present invention and a flame retardant mechanism accordingly.
  • the anionic nanoclay which is a small layered material, fills the space between the dispersed cationic nanoclays during combustion of the organic nanoclay-foaming compound-polymer composite according to the present invention, thereby effectively contacting with air. It is possible to make the formation of char more easily by blocking, thereby increasing thermal stability and mechanical properties at the same time, minimizing the use of foaming compound for reducing flame retardancy and calorific value, thereby improving thermal stability and It is effective to maintain mechanical properties.
  • the organic nanoclay-polymer composite based on 100 parts by weight of the polymer, about 0.1 to about 50 parts by weight of the organic cationic nanoclay, and about 0.1 to about 50 to the organic anionic nanoclay It may include 50 parts by weight, but may not be limited thereto.
  • the content of the organicated cationic nanoclay is about 0.1 to about 50 parts by weight, about 0.1 to about 40 parts by weight, about 0.1 to about 30 parts by weight, and about 0.1 to about 100 parts by weight of the polymer.
  • the content of the organic anionic nanoclay is about 0.1 to about 50 parts by weight, about 0.1 to about 40 parts by weight, about 0.1 to about 30 parts by weight, about 0.1 to about 20 parts by weight, based on 100 parts by weight of the polymer, About 0.1 to about 10 parts by weight, or about 0.1 to about 5 parts by weight, but may not be limited thereto.
  • the content of the foam compound is about 0.1 to about 50 parts by weight, about 0.1 to about 20 parts by weight, about 0.1 to 100 parts by weight of the polymer. To about 15 parts by weight, preferably about 0.1 to about 10 parts by weight, or about 0.1 to about 5 parts by weight, but may not be limited thereto.
  • the cationic nanoclay is montmorillonite, bentonite, hectorite, saponite, beidelite, nontronite ( nontronite, swellable mica, vermicullite, synthetic mica, kanemite, magadite, kenyaite, kaolinite, smectite , Illite, chlorite, muscovite, pyrophyllite, antigorite, glauconite, vermiculite, sepiolite , Imogolite, sockockite, nacrite, anoxite, sericite, ledikite, chrysotile, antigorite, and these Stratified from the group consisting of It may include silicate, but may not be limited thereto.
  • the cationic nanoclay uses swellable clays such as smectite-based clays, and montmorillonite-based clays have many applications.
  • the oxygen forms a tetrahedron around the silicon, the tetrahedron are layered while sharing the vertices, this silicate tetrahedral layer is mainly aluminum ions and oxygen hydroxyl group (-OH -) octahedron made of the octahedron with the It forms an aluminosilicate layer that is enclosed above and below the layer.
  • the montmorillonite structure is called a dioctahedral structure because two of the three aluminum sites of the octahedral layer contain aluminum ions and one is empty. Further, a part of the trivalent aluminum ion octahedron layer Fe 2 +, Ca 2 + of the divalent substituted with ions such structure, that is dissimilar statue substituted (isomorphous substitution), and in the aluminosilicate layer takes on a negative charge. In order to neutralize this negative charge, it has a layered structure containing a cation, that is, Na + , between the aluminosilicate layers.
  • the Na + ions between the aluminosilicate layer and the layers are very hydrophilic, so they swell very well in water, and may be caused by ion exchange or ion-dipole action with other cations or polar ions or molecules, clusters, etc.
  • the intercalation reaction occurs well.
  • the nanocomposites dispersed in the polymer matrix may be synthesized by treating the surface with an organic material having lipophilic properties.
  • the organic agent of the cationic nanoclay is cetyltrimethylammonium salt, tetradecylamine, hexadecylamine, octadecylamine, dimethyl distearyl ammonium salt, trimethyl tetradecyl ammonium salt, trimethylhexadecyl ammonium salt, trimethyl Octadecyl ammonium salt, benzyl trimethyl ammonium salt, benzyl triethyl ammonium salt, phenyl trimethyl ammonium salt, dimethyl dioctadecyl ammonium salt, benzalkonium salt, steralconium salt, denatonium salt, cetylpyridinium salt, tetra-n-butylammonium salt, polyquater Nium salt, hexyl ammonium salt, octyl ammonium salt, octadecyl ammonium salt, dioctyl
  • the organic cationic nanoclay, the cationic surfactant is a form inserted between the layers of the cationic nanoclay, they may be bound by the electrostatic attraction, but is not limited thereto It may not be.
  • the organic cationic nanoclay may be to include the following formula (1):
  • Na 0 . 7 (Mg 2.65 Si 4 ) O 10 F 2 is a kind of synthetic nanoclay, and can be replaced with synthetic or natural layered aluminosilicates such as montmorillonite, hectorite, saponite, and the like (C 16 H 33 ) N (CH 3 ) 3 is the cation form of cetyltrimethylammonium and is replaceable with other cationic surfactants, and X is a positive number greater than zero.
  • the organic anionic nanoclay may be to include a layered metal bilayer hydroxide represented by the following formula (2), but may not be limited thereto:
  • M 2+ is a divalent metal cation
  • M 3+ is a trivalent metal cation
  • A is an anion of a negatively charged anionic surfactant of n
  • x is a number from 0 to 1
  • y is a number from 0 to 1
  • n Each represents a positive number.
  • LDH layered double hydroxide used as the anionic nanoclay has a structure containing anions between layers, and representative minerals found in nature are hydrotalcite, Mg 6 Al 2 (OH) 16 CO 3 ⁇ H 2 O], and the LDH may be referred to as a hydrotalcite-like compound.
  • the structure is based on a brucite (Mg (OH) 2 ) layer.
  • LDH layer is a divalent metal cation such as Mg + 2 to the center octa head LAL site, six hydroxyl groups (-OH -) may have a structure in which the unit for a six-fold connection in a two-dimensional manner.
  • LDH in the hydrotalcite structure is slightly different Kalou boehmite some cases having a (Ca 4 Al 2 (OH) 12 CO 3 ⁇ 5H 2 O), LDH and composition is similar to one divalent cation is Ca 2 + has 6 a hydroxyl group (-OH -) and one of water (H 2 O) and has been a structure in which 7 configuration and the other structure is the same.
  • This LDH has the advantage that the composition of the metal ions can be adjusted when a divalent metal cation and a trivalent metal cation are co-precipitated at an appropriate pH.
  • anion exchange ability anionic organic materials, inorganic materials or anionic biomaterials such as DNA, etc. having a specific function are intercalated instead of interlayer anions such as Cl ⁇ and NO 3 ⁇ and applied to various fields.
  • LDH including Mg and Al has no human toxicity, and thus, research on the application as a drug delivery carrier in the pharmaceutical field has been actively reported.
  • LDH may be used as an additive and used as a Cl - ion scavenger in PVC.
  • LDH is effective in reducing calorific value as well as flame retardant because endothermic reaction by dehydration reaction occurs as the temperature rises.
  • LDH has a hydrophilic property because there is a hydroxyl group on the surface of the layer, it is necessary to modify the surface with a hydrophobic organic material to be applied as a flame retardant additive in hydrophobic polymers.
  • the organic agent of the anionic nanoclay alkyl carboxylates such as stearate, palmityate or lauryl acid salts, alkyl sulfate salts such as dodecyl sulfate salt, dodecylbenzenesulfonate
  • alkyl sulfate salts such as dodecyl sulfate salt
  • dodecylbenzenesulfonate It may be, but is not limited to, an anionic surfactant selected from the group consisting of alkylbenzenesulfonate salts such as salts, alkylphosphate salts such as laurylphosphate salts, alkylpolyoxyethylenesulfate salts, and combinations thereof. have.
  • the organic anionic nanoclay, the anionic surfactant is a form inserted between the layers of the layered metal bilayer hydroxide, they may be bound by the electrostatic attraction, but is not limited thereto It may not be.
  • the foaming compound ammonium polyphosphate, primary ammonium phosphate (primary ammonium phosphate), secondary ammonium phosphate (secondary ammonium phosphate), ammonium phosphite, melamine phosphate, dimelamine phosphate, melamine fatigue
  • a carbonizing agent selected from the group consisting of pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, trimethylolpropane, trimethylolethane, ditrimethylolpropane, and combinations thereof, This may not be limited.
  • the polymer is polyethylene vinyl acetate (EVA), polypropylene (PP), poly acrylonitrile butadiene styrene (ABS), polyethylene (PE), polyacetylene, polystyrene (PS), poly Urethane (PU), polyamide (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and combinations thereof may be included, but is not limited thereto. have.
  • EVA polyethylene vinyl acetate
  • PP polypropylene
  • ABS poly acrylonitrile butadiene styrene
  • PE polyethylene
  • PS polyacetylene
  • PS poly Urethane
  • PA polyamide
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • a second aspect of the present disclosure is directed to preparing a cationic surfactant-containing solution and an anionic surfactant-containing solution, respectively;
  • the cationic surfactant-containing solution was stirred with a cationic nanoclay-dispersed solution and the anionic surfactant-containing solution was stirred with anionic nanoclay-dispersed solution to form an organic cationic nanoclay and an organic anionic nanoclay.
  • the organic nanoclay-polymer composite according to this aspect, all of the contents described for the first aspect of the present application can be applied.
  • it may further include adding a foaming compound to the organic nanoclay-polymer composite, but may not be limited thereto.
  • the organic nanoclay-polymer composite based on 100 parts by weight of the polymer, about 0.1 to about 50 parts by weight of the organic cationic nanoclay, and about 0.1 to about 50 to the organic anionic nanoclay It may include 50 parts by weight, but may not be limited thereto.
  • the content of the organicated cationic nanoclay is about 0.1 to about 50 parts by weight, about 0.1 to about 40 parts by weight, about 0.1 to about 30 parts by weight, and about 0.1 to about 100 parts by weight of the polymer.
  • the content of the organic anionic nanoclay is about 0.1 to about 50 parts by weight, about 0.1 to about 40 parts by weight, about 0.1 to about 30 parts by weight, about 0.1 to about 20 parts by weight, based on 100 parts by weight of the polymer, About 0.1 to about 10 parts by weight, or about 0.1 to about 5 parts by weight, but may not be limited thereto.
  • the content of the foam compound is about 0.1 to about 50 parts by weight, about 0.1 to about 20 parts by weight, about 0.1 to 100 parts by weight of the polymer. To about 15 parts by weight, preferably about 0.1 to about 10 parts by weight, or about 0.1 to about 5 parts by weight, but may not be limited thereto.
  • Nanoclays substituted with organic agents were synthesized using an ion exchange reaction.
  • 16 g of distilled water was added to a 20 L reactor, and while stirring, 320 g of synthetic mica (ME-100, COOP Chemicals) was slowly added and dispersed at 60 ° C. for 6 hours.
  • 320 mmol of cetyltrimethyl ammonium bromide 116.6 g, corresponding to 1 times the cation substitution capacity (CEC) of ME-100
  • CEC cation substitution capacity
  • Sodium stearate (SA, Daejung Chemicals) 0.945 mol (289.6 g) was added to a 20 L reactor containing a mixed solution of 3 L ethanol and 3 L distilled water and heated to 65 °C to make a SA solution.
  • the complex in which the organic cationic clay (CTA-ME) and the organic anionic clay (SA-LDH) were dispersed in a polymer was synthesized in various ways using a solution-blending method.
  • Synthesis was carried out in the same manner as in the method for preparing PP-LDH1ME2 complex of 1), except that 0.0 g of SA-LDH and 1.0 g of CTA-ME were used.
  • the polymer solution in which the organic nanoclay-polymer composite was dispersed was precipitated in 400 mL ethanol solution.
  • the precipitate was separated using a filter and vacuum dried at 80 ° C. to synthesize a SA-LDH 1% / CTA-ME 2% / EVA composite.
  • Synthesis was carried out in the same manner as in the method for preparing EVA-LDH1ME2 complex of 13), except that 0.0 g of SA-LDH and 0.8 g of CTA-ME were used.
  • Synthesis was performed in the same manner as in the method for preparing EVA-LDH1ME2 complex of 13), except that 0.0 g of SA-LDH and 1.0 g of CTA-ME were used.
  • the thermal stability test was carried out using the organic nanoclay-polymer composite prepared in Example 1 and a polymer as a control thereof. Thermal analysis tests were performed using a thermal gravimetric (TG) analyzer (TA Instruments SDT-Q600) at a temperature range of 30 ° C. to 800 ° C. with air flowing at a rate of 200 mL / min.
  • TG thermal gravimetric
  • the thermal stability was observed to improve thermal stability by 25 ° C when 4 wt% of CTA-ME was added in EVA composite containing 1 wt% and 2 wt% of SA-LDH. can do. From this, it can be seen that the thermal stability is greatly improved by synergistic effect when using SA-LDH and CTA-ME simultaneously than when using each layered material in the case of thermal stability.
  • PP itself shows a sharp weight loss due to the combustion reaction between 270 °C to 370 °C
  • the thermal stability of the composite according to the present application is significantly improved TG curve toward the overall high temperature You can see it moved.
  • the weight loss 50% temperature when the SA-LDH 1%, 2% was found to improve the thermal stability about 40 °C.
  • the pyrolysis temperature of the composite having 4 wt% and 5 wt% of only CTA-ME dispersed without SA-LDH is increased by about 23 ° C. It can be seen that the SA-LDH has a significant effect on the thermal stability in the PP nanocomposite.
  • the elastic modulus and tensile strength which are mechanical properties of SA-LDH / CTA-ME / EVA nanocomposites of various compositions, are increased as the amount of CTA-ME increases when SA-LDH is 1 wt%.
  • SA-LDH when the content of CTA-ME reaches 3 wt%, it tends to converge.
  • SA-LDH is 2 wt%, both values slightly increase as the amount of CTA-ME increases, but it does not show a big change. From these results, it can be seen that the thermal stability and mechanical properties are the highest in the nanocomposite synthesized by adding 1 wt% of SA-LDH and 4 wt% of CTA-ME to EVA.
  • the CTA-ME content is similar to that of the EVA nanocomposite.
  • the modulus of elasticity increases with the increase, but it tends to converge when the content of CTA-ME reaches 3 wt%.
  • the modulus of elasticity is lower than that of the PP nanocomposite having a composition of 1 wt% of SA-LDH, but increases slightly as the amount of CTA-ME increases.
  • the organic nanoclays CTA-ME and SA-LDH do not affect the elastic modulus of PP when forming the PP nanocomposite. From these results, it can be seen that the thermal stability and the mechanical properties are the highest in the PP nanocomposite synthesized by adding 1 wt% of SA-LDH and 4 wt% of CTA-ME.
  • a cone calorimeter (concalimeter) test was performed using the organic nanoclay-polymer nanocomposite prepared in Example 1 and a polymer as a control thereof.
  • the cone calorimeter test uses a cone calorimeter to measure square shaped specimens ejected to a size of 10 ⁇ 10 cm 2 .
  • the cone calorimeter test method can measure the flame retardant properties of a material such as the heat release rate, the maximum heat release rate, the total heat release rate over a certain period of time, and the ignition time when the material is placed under constant radiant heat conditions. Test method.
  • the maximum heat release rate is the most important item in evaluating fire safety for a given material.
  • EVA has a maximum heat release peak of 1,863.1 kW / m 2
  • EVA nanocomposite containing 1 wt% SA-LDH EVA nanocomposite containing 4 wt% CTA-ME, and 1 wt% SA-LDH and CTA- EVA nanocomposites containing 4 wt% ME showed 1,855.6 kW / m 2 , 892.8 kW / m 2 , and 658.7 kW / m 2 , respectively.
  • the maximum heat release rate is significantly reduced in EVA nanocomposites containing CTA-ME, which is a cationic nanoclay compared to pure EVA.
  • the EVA nanocomposite containing 1 wt% of SA-LDH and 4 wt% of CTA-ME was found to significantly reduce the maximum heat release rate compared to the EVA nanocomposite containing only 4 wt% of CTA-ME. It can be seen that the flame retardant performance can be improved.
  • Example 2 intumescent-containing organic Nanoclay -Polymer Composite
  • SA-LDH / CTA-ME / EVA nanocomposites were synthesized by adding 1 wt% SA-LDH and 4 wt% CTA-ME. Specifically, 0.8 g of CTA-ME and 0.2 g of SA-LDH were added to 80 mL of toluene, and dispersed at 100 ° C. for 12 hours. 20 g of EVA polymer was added to a 120 mL organic solvent and dissolved at 100 ° C., and the mixture was added to the organic solvent in which SA-LDH and CTA-ME were dispersed and stirred at 100 ° C. for 10 hours.
  • Exolit-AP-422 (ammonium polyphosphate), which are foaming compounds, were added thereto, followed by further stirring at 100 ° C. for 2 hours. It was.
  • the polymer solution thus synthesized was precipitated in 400 mL ethanol solution. The precipitate was separated using a filter and vacuum dried at 80 ° C. to synthesize a foamed compound / SA-LDH / CTA-ME / EVA nanocomposite.
  • SA-LDH / CTA-ME / PP nanocomposites were synthesized by adding 1 wt% of SA-LDH and 3 wt% of CTA-ME. Specifically, 0.6 g of CTA-ME and 0.2 g of SA-LDH were added to 80 mL of xylene, and dispersed at 120 ° C. for 12 hours. 20 g of PP was added to 120 mL xylene and dissolved at 120 ° C., and the mixture was added to an organic solvent in which SA-LDH and CTA-ME were dispersed and stirred at 120 ° C. for 10 hours.
  • the thermal stability test was performed using an organic nanoclay-polymer composite containing the foaming compound (intumescent) prepared in Example 2 and a polymer as a control thereof.
  • the thermostability test was carried out using a thermogravimetric analyzer (TA Instruments SDT-Q600) at a temperature range of 30 ° C. to 800 ° C. while flowing air at a rate of 200 mL / min.
  • TA Instruments SDT-Q600 thermogravimetric analyzer
  • the thermal stability is 1 wt% SA-LDH or 4 wt% CTA-ME based on a temperature of 50% weight loss. When included only tends to be lower than that.
  • the thermal stability is about 42 ° C. compared to the PP in the PP-LDH1ME3 composite based on a temperature of 50% by weight.
  • the thermal stability was improved, and when the 5 wt% foaming compound was added, the thermal stability was improved at about 54 ° C and about 70 ° C when the 10% foaming compound was added.
  • the thermal stability showed a tendency of slightly lowering to about 54 ° C. From this, it can be seen that the thermal stability is maximized when the 10 wt% foaming compound is added.
  • the mechanical properties test for the polymer itself was carried out using the organic nanoclay-polymer composite containing the foaming compound prepared in Example 2 and the control [Universal Testing Machine (UTM; Zwick)], and the results are shown in FIG. 8. .
  • E-modulus and tensile strength of the specimens (PP-I5, PP-I10, PP-I20) in which the foaming compound was added to the PP itself were found to be almost unchanged when compared to the PP itself. It could be seen that there was no change even if the addition amount of the foaming compound changed.
  • PP-LDH1ME3 composites have improved modulus of elasticity compared to PP itself, especially when 5% to 20% of foamed compound (I) is added to PP-LDH1ME3 nanocomposites. You can see the improvement. In particular, similar values of elastic modulus were obtained when 5 wt% of the foaming compound was added and 10 wt% of the foaming compound. The elastic modulus value was larger than that of 20 wt% of the foaming compound. . These results confirm that the organic nanoclay / composite can sufficiently improve the modulus of elasticity compared to the polymer itself despite adding the foaming compound (I) within 20%.
  • the tensile strength is maintained within the experimental error range in the nanocomposite containing the nanocomposite and the foamed compound. Therefore, it can be seen that the mechanical properties are maintained or improved by complexing a polymer such as PP with the nanoclay and the foaming compound.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un complexe organique nanoargile-polymère et un procédé de production dudit complexe organique nanoargile-polymère, dans lequel le complexe organique nanoargile-polymère contient une nanoargile cationique organifiée, une nanoargile anionique organifiée, et un polymère.
PCT/KR2015/012489 2014-11-19 2015-11-19 Complexe organique nanoargile-polymère et son procédé de production WO2016080789A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110627470A (zh) * 2019-11-01 2019-12-31 新化县天马建筑新材料科技有限公司 一种双网络增强复合快干凝胶水泥材料及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101867938B1 (ko) 2016-12-30 2018-07-17 주식회사 효성 장기내열안정성이 우수한 폴리케톤과 나노클레이 조성물
KR101993718B1 (ko) * 2017-07-20 2019-06-27 서울대학교산학협력단 난연시트 및 그 제조 방법과 그 난연시트가 적용된 ｃｌｔ
WO2019164311A1 (fr) * 2018-02-21 2019-08-29 서울대학교산학협력단 Composite polymère biodégradable
KR102046264B1 (ko) * 2018-11-27 2019-11-19 노우준 재생 폴리염화비닐 컴파운드 조성물 및 이의 제조방법
KR102146320B1 (ko) * 2019-12-10 2020-08-21 ㈜웰사이언픽랩 유기나노점토 기반의 발수성 및 발유성 나노코팅용 조성물
KR102361664B1 (ko) * 2020-05-25 2022-02-10 전남대학교산학협력단 알킬 4가 암모늄의 제조방법, 유기화 나노 클레이의 제조방법 및 가스배리어성 고분자-점토 하이브리드 나노복합체의 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6815489B1 (en) * 1999-07-13 2004-11-09 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Nanocomposite coatings
KR20080110591A (ko) * 2006-02-24 2008-12-18 아크조 노벨 엔.브이. 난연성 복합 물질
US20090317627A1 (en) * 2008-06-24 2009-12-24 Chung Yuan Christan University Modified clay and clay-polymer composite
KR101036220B1 (ko) * 2002-10-31 2011-05-20 더 보잉 컴파니 내화재
KR20130142214A (ko) * 2012-06-14 2013-12-30 주식회사 베스텍 폴리올레핀계 수지 조성물 및 그 제조방법

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101090844B1 (ko) * 2009-05-13 2011-12-08 자동차부품연구원 우수한 기계적 물성을 갖는 고분자-클레이 나노복합체의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6815489B1 (en) * 1999-07-13 2004-11-09 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Nanocomposite coatings
KR101036220B1 (ko) * 2002-10-31 2011-05-20 더 보잉 컴파니 내화재
KR20080110591A (ko) * 2006-02-24 2008-12-18 아크조 노벨 엔.브이. 난연성 복합 물질
US20090317627A1 (en) * 2008-06-24 2009-12-24 Chung Yuan Christan University Modified clay and clay-polymer composite
KR20130142214A (ko) * 2012-06-14 2013-12-30 주식회사 베스텍 폴리올레핀계 수지 조성물 및 그 제조방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110627470A (zh) * 2019-11-01 2019-12-31 新化县天马建筑新材料科技有限公司 一种双网络增强复合快干凝胶水泥材料及其制备方法
CN110627470B (zh) * 2019-11-01 2020-05-05 新化县天马建筑新材料科技有限公司 一种双网络增强复合快干凝胶水泥材料及其制备方法

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