WO2016080789A1

WO2016080789A1 - Organic nanoclay-polymer composite and method for preparing same

Info

Publication number: WO2016080789A1
Application number: PCT/KR2015/012489
Authority: WO
Inventors: 최진호; 양재훈; 박대환; 이지희; 류현주
Original assignee: 이화여자대학교 산학협력단
Priority date: 2014-11-19
Filing date: 2015-11-19
Publication date: 2016-05-26
Also published as: KR20170083009A; KR20160059990A; KR101840206B1

Abstract

The present invention relates to an organic nanoclay-polymer composite and a method for preparing the organic nanoclay-polymer composite, wherein the organic nanoclay-polymer composite includes an organomodified cationic nanoclay, an organomodified anionic nanoclay, and a polymer.

Description

Organic Nanoclay-Polymer Complexes and Methods for Making the Same

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.

There are a variety of methods for flame retarding the polymer, there is a method for producing a heat-resistant polymer by changing the molecular structure, or adding a material having a flame retardant component to the polymer. Inorganic flame retardants are most commonly used, and examples thereof include halogen compounds and phosphorus flame retardants. Halogen-based compounds have the advantage of imparting excellent flame retardancy, but has the disadvantage of generating harmful gases to the human body with hydrogen halide upon combustion. Due to this problem, many non-halogen-based materials have been recently developed.

On the other hand, it is important to minimize the degradation of the thermal stability, physical properties by the added flame retardant. For this reason, polymer composites with various inorganic substances have been developed, and many studies have reported that proper dispersion of nanoclays in polymer materials improves flame retardant performance by a certain level or more (Korea Patent Publication No. 10-2005-0112144). Etc). The mechanism of flame retardant properties of nanoclays is that volatile organic low-molecular substances produced by thermal oxidation reaction in the event of fire due to the high aspect ratio of nanoclay particles made by effective nanoclay exfoliation increase the contact area with the polymer. It is exerted through the effect of effectively delaying the diffusion to the surface. However, since nanoclay is hydrophilic, dispersion in water is excellent but dispersibility in materials such as polymers is poor.

In addition, as 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.

However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

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. Preparing each; And dispersing the organic cationic nanoclay and organic anionic nanoclay in a polymer to prepare an organic nanoclay-polymer composite according to the first aspect.

In one embodiment of the invention, 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 By dispersing a kind of organic nanoclay to prepare an organic nanoclay-polymer composite, 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.

2A and 2B are thermogravimetric analysis results of an organic nanoclay-polymer composite and a polymer (EVA) 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.

4A and 4B are thermogravimetric analysis results of an organic nanoclay-polymer composite and a polymer (PP) according to one 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.

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.

7A and 7B are thermogravimetric analysis results of a polymer and an organic nanoclay-polymer composite according to the presence or absence of a foaming compound according to one embodiment of the present application.

8 is a result of measuring the elastic modulus and tensile strength of the polymer and the various organic nanoclay-polymer composite according to the foam compound according to an embodiment of the present application.

Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a portion is "connected" to another portion, this includes not only "directly connected" but also "electrically connected" with another element in between. do.

Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless specifically stated otherwise.

As used throughout this specification, the terms "about", "substantially" and the like are used at, or in the sense of, numerical values when a manufacturing and material tolerance inherent in the stated meanings is indicated, Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers.

As used throughout this specification, the term "step to" or "step of" does not mean "step for."

Throughout this specification, 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.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B."

Throughout this specification, "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.

Hereinafter, embodiments of the present disclosure have been described, but the present disclosure may not be limited thereto.

In one embodiment of the present application, 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.

In one embodiment of the present application, the organic nanoclay-polymer composite may be one having a flame retardant or calorific value reducing effect, but may not be limited thereto.

In one embodiment of the present application, 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. . In particular, (c) 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.

In one embodiment of the present application, 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. For example, 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. 20 parts by weight, about 0.1 to about 10 parts by weight, or about 0.1 to about 5 parts by weight; 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.

In one embodiment of the present application, when the foam compound is further included, 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.

In one embodiment of the present application, 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.

Generally, the cationic nanoclay uses swellable clays such as smectite-based clays, and montmorillonite-based clays have many applications. In the structure, 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. In general, 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. However, in order to synthesize a complex with a high hydrophobic polymer, the nanocomposites dispersed in the polymer matrix may be synthesized by treating the surface with an organic material having lipophilic properties.

In one embodiment of the present application, 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 diethyl ammonium salt, dioctadecyl dimethyl ammonium salt, hexyl hydroxyethyl ammonium salt, dodecyl hydroxyethyl dimethyl ammonium salt, octadecyl hydroxyethyl dimethyl ammonium salt, octyl carboxyethyl ammonium salt, Dodecylcarboxyethyldimethylammonium salt, hexadecyl Carboxyl dimethylammonium salt, octadecylcarboxyethyldimethylammonium salt, dodecyl mercaptoethylmethylammonium salt, hexadecyl mercaptoethyldimethylammonium salt, tetraethylphosphonium salt, triethylbenzylphosphonium salt, tri-n-butylbenzylphosphophosphate It may include, but is not limited to, cationic surfactants selected from the group consisting of nium salts, and combinations thereof.

In one embodiment of the present application, 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.

In one embodiment of the present application, the organic cationic nanoclay, specifically, may be to include the following formula (1):

[Formula 1]

Na _0.7 (Mg _2.65 Si ₄ ) O ₁₀ F ₂ [(C ₁₆ H ₃₃ ) N (CH ₃ ) ₃ ] _x ;

In 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.

In one embodiment of the present application, 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:

[Formula 2]

[M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] [A ^n- ] _{x / n} y (H ₂ O);

Wherein 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 and 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. Part of the divalent cation such as Mg ² ⁺ is substituted with a trivalent cation such as Al ³ ⁺ and the LDH layer has a positive charge, carbonate (CO ₃ ^2- ) and between the layers to neutralize the layer charges generated It has a layered structure containing the same anion. LDH during 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. In addition, since it has an 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. In particular, 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. In polymer applications, LDH may be used as an additive and used as a Cl ^- ion scavenger in PVC. In particular, LDH is effective in reducing calorific value as well as flame retardant because endothermic reaction by dehydration reaction occurs as the temperature rises. On the other hand, like cationic nanoclays, 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.

In one embodiment of the present application, 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 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.

In one embodiment of the present application, 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.

In one embodiment of the present invention, 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 One selected from the group consisting of phosphate, tricresyl phosphate, and combinations thereof; Or a carbonizing agent selected from the group consisting of pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, trimethylolpropane, trimethylolethane, ditrimethylolpropane, and combinations thereof, This may not be limited.

In one embodiment of the present application, 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.

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. Preparing each; And dispersing the organic cationic nanoclay and organic anionic nanoclay in a polymer to prepare an organic nanoclay-polymer composite according to the first aspect. With respect to 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.

In one embodiment of the present application, it may further include adding a foaming compound to the organic nanoclay-polymer composite, but may not be limited thereto.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are only provided to help understanding of the present application, and the contents of the present application are not limited to the following Examples.

[실시예] EXAMPLE

실시예 1: 유기 나노클레이-고분자 복합체 제조Example 1 Preparation of Organic Nanoclay-Polymer Composites

1-1. 유기화 양이온성 나노클레이의 제조1-1. Preparation of Organicized Cationic Nanoclays

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. To this, 320 mmol of cetyltrimethyl ammonium bromide (116.6 g, corresponding to 1 times the cation substitution capacity (CEC) of ME-100) and 3 L of ethanol were added to perform an ion exchange reaction at 60 ° C. for 10 hours. Proceeded. After the reaction, the stirring was stopped and after waiting for 10 minutes, ME-100 (CTA-ME hybrid) surface-modified with cetyltrimethyl ammonium floated on the water to separate the water and the layer. The clear solution below was removed using a transfer pump and a glass tube. Thereafter, the CTA-ME hybrid was filtered, stirred in 10 L of distilled water at 60 ° C., redispersed, and then separated from each other to remove the transparent solution including the NaBr salt below, and lyophilized to form an organic cationic nanoparticle. Clay the CTA-ME hybrid was prepared.

1-2. 유기화 음이온성 나노클레이의 제조1-2. Preparation of Organicized Anionic Nanoclays

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 ℃ to make a SA solution. The aqueous solution of 0.3 M magnesium chloride (365.9 g) and 0.15 M aluminum chloride (217.3 g) in the SA solution ([Mg ² ⁺ ] / [Al ³ ⁺ ] = 2, total metal concentration = 0.3 M) 6 L and 1.5 M NaOH solution were slowly added dropwise at the same time to coprecipitation while maintaining the pH at 10, and after completion of the titration, the reaction was carried out at 65 ° C. for 20 hours. After the reaction was completed, the precipitate was separated by phase separation, the solution below was filtered, filtered, and then dispersed in distilled water at 65 ° C., followed by washing with water. Finally, the filtered white precipitate was lyophilized to synthesize SA-LDH.

1-3. 유기 나노클레이-고분자 복합체의 제조1-3. Preparation of Organic Nanoclay-Polymer Composites

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.

1) SA-1) SA- LDHLDH 1% / One% / CTACTA -ME 2% / 폴리프로필렌(PP) 복합체 [PP--ME 2% / Polypropylene (PP) Composite [PP- LDH1ME2LDH1ME2 ]]

0.2 g of SA-LDH was added to 40 mL of xylene, and dispersed at 120 ° C., 0.4 g of CTA-ME was added to 40 mL of xylene, and dispersed at 120 ° C. for 24 hours. Thereafter, 20 g polypropylene polymer was added to 120 mL xylene and dissolved at 120 ° C., and the solution containing the SA-LDH and CTA-ME dispersed therein was added thereto and stirred at 120 ° C. for 24 hours. Organic nanoclay-polymer complexes were formed. The polymer solution in which the organic nanoclay-polymer complex 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% / PP composite.

2) SA-2) SA- LDHLDH 1% / One% / CTACTA -ME 3% / PP 복합체 제조-ME 3% / PP Composite

Except for using 0.6 g of CTA-ME was synthesized in the same manner as the PP-LDH1ME2 composite method of 1).

3) SA-3) SA- LDHLDH 1% / One% / CTACTA -ME 4% / PP 복합체 제조-ME 4% / PP Composite

Except for using 0.8 g of CTA-ME was synthesized in the same manner as the PP-LDH1ME2 complex method of 1).

4) SA-4) SA- LDHLDH 1% / One% / CTACTA -ME 5% / PP 복합체 제조-ME 5% / PP Composite

Except for using 1.0 g of CTA-ME was synthesized in the same manner as the PP-LDH1ME2 composite method of 1).

5) SA-5) SA- LDH LDH 2% / 2% / CTACTA -ME 1% / PP 복합체 제조-ME 1% / PP Composite

0.4 g of SA-LDH was used, and 0.2 g of CTA-ME was used to synthesize the same method as for preparing the PP-LDH1ME2 complex of 1).

6) SA-6) SA- LDH LDH 2% / 2% / CTACTA -ME 2% / PP 복합체 제조-ME 2% / PP Composite

Except for using 0.4 g of SA-LDH was synthesized in the same manner as in the PP-LDH1ME2 composite method of 1).

7) SA-7) SA- LDH LDH 2% / 2% / CTACTA -ME 3% / PP 복합체 제조-ME 3% / PP Composite

Except that 0.4 g of SA-LDH and 0.6 g of CTA-ME were used, the synthesis was carried out in the same manner as in the preparation method of PP-LDH1ME2 complex of 1).

8) SA-8) SA- LDH LDH 2% / 2% / CTACTA -ME 4% / PP 복합체 제조-ME 4% / PP Composite

Except that 0.4 g of SA-LDH and 0.8 g of CTA-ME were used, the synthesis was carried out in the same manner as in the preparation method of PP-LDH1ME2 complex of 1).

9) SA-9) SA- LDHLDH 1% / One% / CTACTA -ME 0% / PP 나노복합체 제조-ME 0% / PP Nanocomposite

Except for using 0.0g of CTA-ME was synthesized in the same manner as the PP-LDH1ME2 composite method of 1).

10) SA-10) SA- LDH LDH 2% / 2% / CTACTA -ME 0% / PP 복합체 제조-ME 0% / PP Composite

Except that 0.4 g of SA-LDH and 0.0 g of CTA-ME were used, the synthesis was carried out in the same manner as in the preparation of the PP-LDH1ME2 complex of 1).

11) SA-11) SA- LDH LDH 0% / 0% / CTACTA -ME 4% / PP 복합체 제조-ME 4% / PP Composite

Except that 0.0 g of SA-LDH and 0.8 g of CTA-ME were used, the synthesis was carried out in the same manner as in the preparation method of PP-LDH1ME2 complex of 1).

12) SA-12) SA- LDH LDH 0% / 0% / CTACTA -ME 5% / PP 복합체 제조-ME 5% / PP Composite

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.

13) SA-13) SA- LDHLDH 1% / One% / CTACTA -ME 2% / -ME 2% / EVAEVA 복합체 제조 [ Composite Preparation EVAEVA -- LDH1ME2LDH1ME2 ]]

0.2 g of SA-LDH was added to 40 mL of toluene and dispersed at 100 ° C., 0.4 g of CTA-ME was added to 40 mL of toluene and dispersed at 100 ° C. for 24 hours. Thereafter, 20 g of ethylene vinyl acetate (EVA) polymer was added to 120 mL toluene and dissolved at 100 ° C, and the SA-LDH dispersion solution and the CTA-ME dispersion solution were added thereto while stirring, followed by stirring at 100 ° C for 24 hours. Thereby forming an organic nanoclay-polymer complex. Thereafter, 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.

14) SA-14) SA- LDHLDH 1% / One% / CTACTA -ME 3% / -ME 3% / EVAEVA 복합체 제조 Composite manufacturing

Except for using 0.6 g of CTA-ME was synthesized in the same manner as in the EVA-LDH1ME2 production method of 13).

15) SA-15) SA- LDHLDH 1% / One% / CTACTA -ME 4% / -ME 4% / EVAEVA 복합체 제조 Composite manufacturing

Except for using 0.8 g of CTA-ME was synthesized in the same manner as in the EVA-LDH1ME2 production method of 13).

16) SA-16) SA- LDHLDH 1% / One% / CTACTA -ME 5% / -ME 5% / EVAEVA 복합체 제조 Composite manufacturing

Except for using 1.0 g of CTA-ME was synthesized in the same manner as in the EVA-LDH1ME2 composite method of 13).

17) SA-17) SA- LDH LDH 2% / 2% / CTACTA -ME 1% / -ME 1% / EVAEVA 복합체 제조 Composite manufacturing

Except that 0.4 g of SA-LDH and 0.2 g of CTA-ME were used, the synthesis was carried out in the same manner as in the preparation of the EVA-LDH1ME2 complex of 13).

18) SA-18) SA- LDH LDH 2% / 2% / CTACTA -ME 2% / -ME 2% / EVAEVA 복합체 제조 Composite manufacturing

Except for using 0.4 g of SA-LDH was synthesized in the same manner as in the EVA-LDH1ME2 composite method of 13).

19) SA-19) SA- LDH LDH 2% / 2% / CTACTA -ME 3% / -ME 3% / EVAEVA 복합체 제조 Composite manufacturing

Except that 0.4 g of SA-LDH and 0.6 g of CTA-ME were used, the synthesis was carried out in the same manner as in the preparation of the EVA-LDH1ME2 complex of 13).

20) SA-20) SA- LDH LDH 2% / 2% / CTACTA -ME 4% / -ME 4% / EVAEVA 복합체 제조 Composite manufacturing

Except that 0.4 g of SA-LDH and 0.8 g of CTA-ME were synthesized in the same manner as in the method for preparing EVA-LDH1ME2 complex of 13).

21) SA-21) SA- LDHLDH 1% / One% / CTACTA -ME 0% / -ME 0% / EVAEVA 복합체 제조 Composite manufacturing

Except for using 0.0 g of CTA-ME was synthesized in the same manner as in the EVA-LDH1ME2 composite method of 13).

22) SA-22) SA- LDH LDH 2% / 2% / CTACTA -ME 0% / -ME 0% / EVAEVA 복합체 제조 Composite manufacturing

Except that 0.4g of SA-LDH and 0.0g of CTA-ME were used, the synthesis was carried out in the same manner as in the EVA-LDH1ME2 preparation method of 13).

23) SA-23) SA- LDH LDH 0% / 0% / CTACTA -ME 4% / -ME 4% / EVAEVA 복합체 제조 Composite manufacturing

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.

24) SA-24) SA- LDH LDH 0% / 0% / CTACTA -ME 5% / -ME 5% / EVAEVA 복합체 제조 Composite manufacturing

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.

실험예 1: 열적 안정성시험 Experimental Example 1: Thermal Stability Test

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.

2A and 2B, in the case of the SA-LDH / CTA-ME / EVA composite, the EVA itself burns while undergoing an exothermic reaction at about 450 ° C., while the thermal stability of the composite is improved, thereby increasing TG. It can be seen that the curve has moved towards higher temperatures as a whole. Based on 50% of the weight loss, the EVA composite containing SA-LDH has improved thermal stability of 8 ℃ or higher, but the EVA composite containing only CTA-ME without SA-LDH is pyrolyzed about 4 ℃. You can see that the temperature has risen. Based on the 50% weight loss, 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.

In addition, referring to Figures 4a and 4b, PP itself shows a sharp weight loss due to the combustion reaction between 270 ℃ to 370 ℃, 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. On the basis of the weight loss 50% temperature, when the SA-LDH 1%, 2% was found to improve the thermal stability about 40 ℃. However, it can be seen that 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.

실험예 2: 기계적 물성 시험 Experimental Example 2: Mechanical Property Test

Mechanical properties were tested using a polymer as an organic nanoclay-polymer nanocomposite prepared in Example 1 and a control thereof [Universal Testing Machine (UTM; Zwick)]. Referring to FIGS. 3A and 3B, the modulus of elasticity (E-modulus) tends to increase slightly as the content of CTA-ME in the EVA composite increases and is not significantly affected by the content of SA-LDH. have. Tensile strength tends to increase slightly by the addition of nanoclays (CTA-ME and SA-LDH), but it can be seen that there is no significant difference in the result of the change of the composition.

Specifically, 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%. However, when the content of CTA-ME reaches 3 wt%, it tends to converge. However, when 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.

Meanwhile, referring to FIGS. 5A and 5B, when the SA-LDH / CTA-ME / PP nanocomposite has a mechanical property of 1 wt% SA-LDH, 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%. However, in the PP nanocomposite having a composition of SA-LDH of 2 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. However, it can be seen that 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.

실험예 3: 난연성 평가 (콘칼로리미터 시험) Experimental Example 3: Flame retardancy evaluation (cone calorimeter test)

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. In particular, the maximum heat release rate is the most important item in evaluating fire safety for a given material.

In this experimental example, the EVA polymer itself and the EVA nanocomposite containing 1 wt% SA-LDH, the EVA nanocomposite containing 4 wt% CTA-ME, and the EVA containing 1 wt% SA-LDH and 4 wt% CTA-ME The flame retardant properties of the nanocomposite were evaluated by cone calorimeter spectroscopy and the results are shown in FIG. 6. Pure EVA has a maximum heat release peak of 1,863.1 kW / m ² , whereas 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. It can be seen that the maximum heat release rate is significantly reduced in EVA nanocomposites containing CTA-ME, which is a cationic nanoclay compared to pure EVA. In particular, 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.

실시예Example 2: 발포 화합물(intumescent)-함유 유기 2: intumescent-containing organic 나노클레이Nanoclay -고분자 복합체 제조-Polymer Composite

2-1. 발포 화합물-유기 2-1. Foaming Compound-Organic 나노클레이Nanoclay -- EVAEVA 복합체 제조 Composite manufacturing

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. 1 g (5 wt%), 2 g (10 wt%), and 4 g (20 wt%) of 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.

2-2. 발포 화합물 함유-유기 나노클레이-PP 복합체 제조2-2. Preparation of Foamed Compound-Containing Organic Nanoclay-PP Composites

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. 1 g (5 wt%), 2 g (10 wt%), and 4 g (20 wt%), respectively, of the foaming compound Exolit-AP-422 (ammonium polyphosphate) were added thereto for an additional 2 hours at 120 ° C. Stirred. The polymer solution thus synthesized was precipitated in 400 mL ethanol solution. The precipitate was separated using a filter and dried in vacuo at 80 ° C. to synthesize foamed compound (I) / SA-LDH / CTA-ME / PP nanocomposites.

실험예 3: 열적 안정성시험Experimental Example 3: Thermal Stability Test

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. Referring to FIG. 7A, in the case of the foamed compound / SA-LDH / CTA-ME / EVA composite, 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. This translates to poor thermal stability as the foam compound material decomposes at a temperature lower than the temperature at which EVA decomposes. On the other hand, when the 5 wt% to 20 wt% foaming compound (I) was added, the effect on thermal stability was hardly seen.

Referring to FIG. 7B, in the case of the foamed compound / SA-LDH / CTA-ME / PP composite, 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. However, when 20 wt% of the 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.

실험예 4: 기계적 물성 시험Experimental Example 4: Mechanical Property Test

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. However, 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%.

However, it can be seen that 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.

The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application. .

Claims

Organized Cationic Nanoclays, Organized Anionic Nanoclays, and Polymers

Comprising, organic nanoclay-polymer composite.
The method of claim 1,

The organic nanoclay-polymer composite will have a flame retardant or calorific value reducing effect, organic nanoclay-polymer composite.
The method of claim 1,

The organic nanoclay-polymer composite further comprising a foaming compound.
The method of claim 1,

To about 100 parts by weight of the polymer, the organic nanoclay-polymer composite comprising 0.1 to 50 parts by weight of the organic cationic nanoclay and 0.1 to 50 parts by weight of the organic anionic nanoclay.
The method of claim 3, wherein

The content of the foaming compound is 0.1 to 50 parts by weight, based on 100 parts by weight of the polymer, organic nanoclay-polymer composite.
The method of claim 1,

The cationic nanoclay may be montmorillonite, bentonite, hectorite, saponite, bidelite, nontronite, swellable mica, vermiculite, synthetic mica, cannemite, margotite, kenyatite, kaolinite, smectite , Illite, chlorite, muscobite, pyrophyllite, antigorite, halostone, vermiculite, sepiolite, imogolite, sobokite, nacrite, anoxite, biotite, readykite, hot stone, antigorite, And a layered silicate selected from the group consisting of, organic nanoclay-polymer composite.
The method of claim 1,

The organic agent of the cationic nanoclay is cetyltrimethylammonium salt, tetradecylamine, hexadecylamine, octadecylamine, dimethyl distearyl ammonium salt, trimethyl tetradecyl ammonium salt, trimethyl hexadecyl ammonium salt, trimethyl octadecyl ammonium salt, benzyl trimethyl ammonium salt, Benzyltriethylammonium salt, phenyltrimethylammonium salt, dimethyldioctadecylammonium salt, benzalkonium salt, steralconium salt, denatonium salt, cetylpyridinium salt, tetra-n-butylammonium salt, polyquaternium salt, hexyl ammonium salt, octyl ammonium salt, Octadecyl ammonium salt, dioctyl diethyl ammonium salt, dioctadecyl dimethyl ammonium salt, hexyl hydroxyethyl ammonium salt, dodecyl hydroxyethyl dimethyl ammonium salt, octadecyl hydroxyethyl dimethyl ammonium salt, octyl carboxyethyl ammonium salt, dodecyl carboxyethyl dimethyl ammonium salt, hexa Decylcarboxyethyl dimethylammonium salt Octadecylcarboxyethyldimethylammonium salt, dodecyl mercaptoethylmethylammonium salt, hexadecyl mercaptoethyldimethylammonium salt, tetraethylphosphonium salt, triethylbenzylphosphonium salt, tri-n-butylbenzylphosphonium salt, and these An organic nanoclay-polymer composite, comprising a cationic surfactant selected from the group consisting of combinations.
The method of claim 7, wherein

The organic cationic nanoclay is an organic nanoclay-polymer composite, wherein the cationic surfactant is a form inserted between the layers of the cationic nanoclay.
The method of claim 1,

The organic anionic nanoclay is an organic nanoclay-polymer composite, comprising a layered metal bilayer hydroxide represented by the following formula (2):

[Formula 2]

[M 2+ 1-x M 3+ x (OH) 2 ] [A n- ] x / n y (H 2 O);

Wherein 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 and n Each represents a positive number.
The method of claim 1,

The organicizing agent of the anionic nanoclay is selected from the group consisting of stearates, alkylcarboxylates, alkylsulfate salts, alkylbenzenesulfonate salts, alkylphosphate salts, alkylpolyoxyethylenesulfate salts, and combinations thereof. It is an anionic surfactant, organic nanoclay-polymer composite.
The method of claim 9,

The organic anionic nanoclay is an organic nanoclay-polymer composite, wherein the anionic surfactant is inserted in the interlayer of the layered metal bilayer hydroxide.
The method of claim 3, wherein

The blowing compound is selected from the group consisting of ammonium polyphosphate, primary ammonium phosphate, secondary ammonium phosphate, ammonium phosphite, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, tricresyl phosphate, and combinations thereof. that; or

Organic nano, comprising a carbonizing agent selected from the group consisting of pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, trimethylolpropane, trimethylolethane, ditrimethylolpropane, and combinations thereof Clay-polymer complex.
The method of claim 1,

The polymer is a group consisting of polyethylene vinyl acetate, polypropylene, poly acrylonitrile butadiene styrene, polyethylene, polyacetylene, polystyrene, polyurethane, polyamide, polyethylene terephthalate, polybutylene terephthalate, and combinations thereof An organic nanoclay-polymer composite, comprising one selected from.
Cationic surfactant-containing solutions and anionic surfactant-containing solutions are prepared, 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. Preparing each; And

14. Dispersing the organic cationic nanoclay and organic anionic nanoclay in a polymer to prepare an organic nanoclay-polymer composite according to any one of claims 1 to 13.

Including,

Method for preparing organic nanoclay-polymer composite.
The method of claim 14,

The method of manufacturing the organic nanoclay-polymer composite further comprising adding a foaming compound to the organic nanoclay-polymer composite.