KR102040089B1

KR102040089B1 - Flame retardant with network structure and preparation method thereof

Info

Publication number: KR102040089B1
Application number: KR1020120115545A
Authority: KR
Inventors: 문현곤; 김태경; 오준록; 백종갑; 김진철; 박기륜; 이동규; 유일환; 조우연
Original assignee: 에스케이씨 주식회사
Priority date: 2012-10-17
Filing date: 2012-10-17
Publication date: 2019-11-06
Also published as: KR20140050149A

Abstract

The flame retardant, in which the plate-shaped filler unit is meshed by organic groups, improves flame retardancy by preventing heat transfer and diffusion in the polymer due to the presence of the plate-shaped filler when dispersed in the polymer. By improving physical properties, it can be used in all areas exposed to fire hazard.

Description

Retardant net flame retardant and its manufacturing method {FLAME RETARDANT WITH NETWORK STRUCTURE AND PREPARATION METHOD THEREOF}

The present invention relates to a mesh flame retardant and a method for producing the same that can impart flame retardancy to a polymer.

Conventionally, flame retardants containing a halogen element have been mainly used as flame retardant materials, but these have an adverse effect on the environment (Japanese Patent Laid-Open Nos. 55-30739 and 8-302102). In particular, bromine-based flame retardant materials have a fatal drawback of generating dioxins, which are toxic gases or carcinogens in fires.

Accordingly, many studies have been conducted to develop non-halogenated flame retardant materials, and monomolecular organophosphorus compounds such as phosphates, phosphonates, and triphenyl phosphate (TPP) have been introduced as non-halogenated flame retardant materials. However, they have a problem that can be easily volatilized or eluted in the polymer after being added to the polymer and not only lead to flame retardancy but also cause secondary contamination.

Japanese Patent Application Laid-Open Nos. 59-202240 and 2-18336 have attempted to improve the above problems by using condensed phosphorus flame retardants using resorcinol, bisphenol derivatives, and the like. In addition, the flame retardancy has another problem that is significantly inferior to the conventional halogen-based flame retardant material.

Japanese Laid-Open Patent Publication No. 55-30739 Japanese Patent Laid-Open No. 8-302102 Japanese Laid-Open Patent Publication No. 59-202240 Japanese Patent Laid-Open No. 2-18336

Accordingly, it is an object of the present invention to provide a new flame retardant and a method for producing the same, which are more environmentally friendly than conventional ones.

According to the above object, the present invention is a plate-shaped filler; And it provides a mesh flame retardant comprising an organic group connecting the plate-shaped filler in a mesh.

According to another object of the present invention, the present invention provides a plate-shaped filler comprising the steps of: combining the other end of the organic modifier (organic modifier) having an unsaturated bond at one end to obtain an organic plated filler; And it provides a method of producing a net flame retardant comprising the step of connecting the terminal having an unsaturated bond of the organic plate-like filler with each other.

In addition, the present invention is a polymer matrix; A plate-shaped filler filled in the polymer matrix; And it provides a flame retardant polymer comprising an organic group connecting the plate-shaped filler in a mesh.

The net flame retardant of the present invention not only improves flame retardancy by preventing heat transfer and diffusion in the polymer due to the presence of a plate-like filler when dispersed in the polymer, but also improves physical properties by interaction of the polymer with an organic agent. As a result, it can be used in all areas exposed to the risk of fire.

Figure 1 schematically shows the chemical structure of the mesh flame retardant according to an example of the present invention.
Figure 2 is a schematic diagram showing an example in which the mesh flame retardant of the present invention is dispersed in a polymer matrix.
3 shows an example of the mechanism by which nanoclay-based materials are organicized by an organizing agent.
4 shows an example of a mechanism in which graphene-based materials are organicized by an organizing agent.
5 is an illustration of a mechanism whereby the ends of an organic agent bound to a plate-like filler are organicized by a polymerization initiator or catalyst.

Hereinafter, a mesh flame retardant according to the present invention will be described in more detail with reference to the accompanying drawings.

The mesh flame retardant of the present invention is characterized in that the plate-shaped fillers 11 and 12 units are mesh-shaped by organic groups 20, as shown in the general chemical structure of FIG.

The plate-shaped filler is not particularly limited, but for example, a nano clay material, a graphene material, or a mixture thereof may be used. More specifically, the nano clay material may be selected from the group consisting of saponite, bentonite, montmorillonite, mica, and mixtures thereof, and the graphene-based material is graphene, graphene oxide, organic graphene, expanded Possible thin film graphite, and mixtures thereof.

In addition, the plate-shaped filler is advantageous in that the area per unit weight is large, for example, the area per unit weight may be 100 to 3000 m ² / g, more specifically may be in the range of 1000 to 2000 m ² / g. have.

In addition, the organic group may mainly mean an aliphatic chain (ie, an acyclic hydrocarbon), and may include, for example, a saturated aliphatic chain or an unsaturated aliphatic chain having 5 to 30 carbon atoms, and more specifically 8 to 20 carbon atoms. Saturated aliphatic chains or unsaturated aliphatic chains. However, the organic group may include inorganic elements in addition to aliphatic chains, and may also include aromatic or non-aromatic carbon rings or hetero rings.

According to one example of the mesh flame retardant of the present invention, the plate-shaped filler is a nano clay-based material, the organic group may have a phosphonium or imidazolium at the end. That is, the anionic atoms of the edge portion of the nanoclay-based material may be connected to each other by ionic bonding with cationic phosphorus or nitrogen at the end of the organic group to form a net form. In addition, the organic group may have a functional group selected from the group consisting of amide, amino, halogen, carboxyl, hydroxy group, ester, ether, cyanate, or a combination thereof between both ends.

According to another example of the mesh flame retardant of the present invention, when the plate-shaped filler is a graphene-based material, the organic group is terminally amide, amino, halogen, carboxyl, hydroxy, ester, ether, cyanate, or a combination thereof. It may have a functional group selected from the group consisting of. In other words, functional groups such as oxides, epoxies, carboxyls, and hydroxy groups present at the edges of graphene-based materials react with amides, amino, halogen, carboxyl, hydroxy, esters, ethers, cyanates, etc. at the end of the organic group, thereby chemically covalently bonding. Etc. can be connected to each other to form a mesh. The organic group may also have a functional group selected from the group consisting of amide, amino, halogen, carboxyl, hydroxy, ester, ether, cyanate, or a combination thereof between both ends.

Hereinafter will be described in detail the manufacturing method of the mesh flame retardant of the present invention.

The net flame retardant of the present invention comprises the steps of: (a) reacting a plate-like filler with an organic agent having an unsaturated bond at one end to bond the plate-shaped filler with the other end of the organic agent, thereby obtaining an organic plated filler; And (b) reacting the organic plated filler with a polymerization initiator or catalyst to connect the terminals having unsaturated bonds of the organic plated filler to each other.

In step (a) of the process of the present invention, the plate-shaped filler may use a material as described above, and the organicizing agent is basically an aliphatic chain, for example a saturated aliphatic chain or unsaturated aliphatic chain having 5 to 30 carbon atoms, More specifically, as a compound containing a saturated aliphatic chain or unsaturated aliphatic chain having 8 to 20 carbon atoms, a compound having an unsaturated bond, i.e., a double bond and / or a triple bond, at one end of the aliphatic chain can be used. The organizing agent may include inorganic elements in addition to aliphatic chains, and may also include aromatic or non-aromatic carbon rings or hetero rings.

In the reaction of step (a), the reaction weight ratio of the plate-shaped filler and the organic agent may be 1: 0.1 to 1:10, more specifically 1: 1 to 1: 2. In addition, the reaction temperature may be 50 to 150 ° C, more specifically 80 to 110 ° C. In addition, the reaction time may be 1 to 24 hours, more specifically 6 to 8 hours.

In one example of step (a) of the present invention, a nano clay-based material is used as the plate-shaped filler, and a compound having an unsaturated bond at one end and a phosphonium or imidazolium at the other end is used as the organicizing agent. Can be. At this time, the nano-clay material may be used as described above.

In addition, examples of the organic agent including phosphonium at the terminal include des-9-enyltriphenylphosphonium bromide represented by the following formula (1), and an organic agent including imidazolium at the terminal. Examples include 3-dec-9-enyl-1,5-dimethyl imidazolium of Formula 2 below, and mixtures thereof are also possible.

Formula 1

Formula 2

As a result, as shown in FIG. 3, through the reaction of step (a), the anionic atoms present at the edges of the individual plate-shaped units of the nanoclay-based material are ionically bonded with the cationic phosphorus or nitrogen atom at the end of the organic agent, Nano clay-based materials may be organic. However, the reaction illustrated in FIG. 3 is only one example, and it is possible to organicize the nano clay-based material through various other reactions.

In another example of step (a) of the present invention, a graphene-based material is used as the plate-shaped filler, and as the organicating agent, an unsaturated bond is used at one end and an amide, amino, halogen, carboxyl, hydroxy, Compounds having a functional group selected from the group consisting of esters, ethers, cyanates, and combinations thereof can be used. At this time, the graphene-based material may be used as described above.

Examples of the organic agent having an amide at the end may include 18-vinyloctadecyl amide of Formula 3, and an example of an organic agent having a halogen at the terminal is 7-vinylheptanoyl chloride of Formula 4 (7-vinylheptanoyl chloride), and examples of the organic agent having a carboxyl group at the terminal may include cucurbic acid of Formula 5; 2-((1R, 2S, 3S) -3-hydroxy-2-(( Z) -pent-2-enyl) cyclopentyl) acetic acid, and an example of an organic agent having amino at the terminal is N- (2-aminoethyl) maleimide (N- (2-aminoethyl) maleimide), and mixtures thereof are also possible.

Formula 3

Formula 4

Formula 5

Formula 6

As a result, as shown in Figure 4, through the reaction of the step (a), functional groups such as oxides, epoxy, carboxyl, hydroxy, etc. present at the edge of the graphene-based material is amide, amino, halogen, carboxyl at the end of the organic agent By chemically bonding to hydroxy, ester, ether, cyanate and the like, the graphene-based material can be organicized with the production of by-product water or acid. However, the reaction illustrated in FIG. 4 is only one example, and it is possible to organicize the graphene-based material through various other reactions.

Next, in step (b) of the method of the present invention, an azo-based polymerization initiator or Grubbs catalyst is used to terminate the terminal having the unsaturated bond of the organic plated filler obtained in step (a). Can be connected to each other.

In the reaction of step (b), the reaction weight ratio of the organic plated filler and the polymerization initiator or catalyst may be 1: 0.001 to 1: 0.1, more specifically 1: 0.01 to 1: 0.05. In addition, the reaction temperature may be 50 to 150 ° C, more specifically 80 to 110 ° C. In addition, the reaction time may be 30 to 360 minutes, or 30 to 180 minutes, and more specifically 60 to 120 minutes.

Specific examples of the azo-based polymerization initiator include azobisisobutyronitrile (AIBN), 2,2'-azobis (4-methoxy-2,4-dimethyl valeronitrile) (2,2'-azobis (4-methoxy-2,4-dimethyl valeronitrile)), 2,2'-azobis (2,4-dimethyl valeronitrile) (2,2'-azobis (2, 4-dimethyl valeronitrile)), 2,2'-azobis (2-methylbutyronitrile) (2,2'-azobis (2-methylbutyronitrile)), 1,1'-azobis (cyclohexane-1- Carbonitrile) (1,1'-azobis (cyclohexane-1-carbonitrile)), 2,2'-azobis (N-butyl-2-methylpropionamide) (2,2'-azobis (N-butyl-2) -methylpropionamide)), and mixtures thereof.

In addition, the Grubbs catalyst may be a primary Grubbs catalyst, a secondary Grubbs catalyst, and a tertiary Grubbs catalyst, each of them or a mixture thereof may be used.

As a result, as shown in FIG. 5, the terminals having unsaturated bonds present in the organicated plate-shaped fillers 31 and 32 obtained in the previous step (a) are connected to each other due to the action of the polymerization initiator or catalyst 40, It can form a flame retardant.

According to another aspect of the present invention, the flame retardant polymer will be described in detail below.

As shown in FIG. 2, the flame retardant polymer of the present invention is characterized in that the plate-shaped fillers 11 and 12 are filled in the polymer matrix 50, and the plate-shaped fillers are connected in a mesh shape by the organic group 20.

Examples of the polymer matrix include polyurethane, polyimide, polyamide, polyester, liquid crystal polymer, and the like.

In addition, the amount of the net flame retardant dispersed in the flame retardant polymer (ie, plate-shaped filler connected in a net by organic groups) may be 1 to 30% by weight based on the total weight of the flame retardant polymer, and more specifically 5 to 15% by weight. have.

According to one example of the method for producing a flame retardant polymer of the present invention, (a) bonding the other end of the organic agent having an unsaturated bond at one end to the plate-shaped filler, to obtain an organicated plate-like filler; (b) connecting the ends having unsaturated bonds of the organic plate-like filler to each other to prepare a net flame retardant; And (c) it may be prepared by a method comprising the step of dispersing the retardant in the polymer.

According to another example of the method for producing a flame retardant polymer of the present invention, (a) bonding the other end of the organic agent having an unsaturated bond at one end to the plate-shaped filler, to obtain an organicated plate-like filler; (b) dispersing the organic plated filler in a polymer; And (c) connecting the terminals having unsaturated bonds of the organicized plate-shaped filler dispersed in the polymer to each other.

As such, the plate-like filler may make a direct primary bond between the plate-shaped filler and the organic agent through an organic treatment, and thus, the dispersion of each plate-shaped filler in the polymer may be advantageous.

The mesh flame retardant of the present invention can be applied to the dispersion or blending of various polymer materials, and the plate-shaped filler in the flame retardant can prevent heat transfer and diffusion in the polymer, thereby providing flame retardancy. In particular, the filler can withstand temperatures of 1000 ° C. or higher, thereby forming a filler film on the surface in the event of a fire, thereby reducing the durability of the fire.

In addition, since a conventional flame retardant is dispersed in a polymer using a dispersant, the composite flame retardant material may not be properly dispersed, thereby lowering the physical properties of the material. According to the present invention, individual filler units may be reticulated through an organic agent. In addition, the filler and the polymer material can improve the physical properties while providing flame retardancy by strengthening the surface bond by the organic agent.

In addition, it is possible to control the distance between the filler and the filler by adjusting the carbon chain containing the aliphatic or aromatic of the organic agent, and can be prepared as a flame-retardant filler capable of high filling depending on the number of organic agents synthesized.

Therefore, the mesh flame retardant and flame retardant polymer of the present invention can be used in all fields exposed to the risk of fire, for example, in building / vehicle or subway materials to reduce the spread of flame or extinguish the flame in case of fire. Can be used for material development.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited to the following examples.

Example 1 Preparation of Organicized Nanoclay-Based Materials

First, to prepare an organic agent, 10 g of triphenylphosphine (93090, fluka) and 10 g of 10-bromo-1-decene (560855, Sigma Aldrich) were added to a tetrahydrofuran solution at 50 ° C. for 24 to 240 hours. Reacted. After the completion of the reaction, n-hexane and diethyl ether were washed with a solution mixed in a volume ratio of 1: 1 and dried to obtain des-9-enyltriphenylphosphonium bromide as an organic agent.

3 g of the organic agent prepared above was dispersed in 100 mL of water, and 10 g of 60% hydrochloric acid solution was added thereto and reacted at 80 ° C. for 1 hour to obtain a chlorinated organic agent solution. Meanwhile, separately, 1 g of nano clay (saponite, kunimine) was dispersed in 100 mL of water to prepare a nano clay solution.

The obtained nanoclay solution was reacted with the chlorinated organic agent solution at 80 ° C. for 4 hours. The reacted material was filtered by centrifugation or reduced pressure, washed with water / ethanol (1: 1, v / v) mixed solution, and the filtration process was repeated again. It was then dried to obtain an organic nanoclay material.

Example 2 Preparation of Organicized Graphene-Based Materials

1 g of thin film graphite (graphite flake, 332461, sigma aldrich) and 2 g of sodium nitrate were added to 100 g of 60% sulfuric acid solution at 0 ° C. for 30 minutes. Thereafter, 10 g of potassium permanganate was added thereto and reacted at 25 ° C. for 4 hours. The reaction solution was washed with 0.1M aqueous hydrogen peroxide solution and then washed with distilled water. The obtained solution was frozen and freeze-dried to obtain graphene oxide.

1 g of the obtained graphene oxide was dispersed well in 100 mL of water, and then, 1 g of an organic agent (N- (2-aminoethyl) maleimide, A2436, TCI Co., Ltd.) was dissolved in 100 mL of ethanol, and the resultant solution was prepared at 12O < 80 > The reaction was carried out for a time. After washing in ethanol and dried to obtain an organic graphene-based material.

Example 3: Preparation of Reticulated Flame Retardant

1 g of the organic nanoclay material prepared in Example 1 and 1 g of the organic graphene material prepared in Example 2 were well dispersed in 200 mL of ethanol, and then 0.005 g of AIBN, a polymerization initiator, was added thereto at 60 ° C. for 6 hours. Reacted for a while.

Thereafter, in order to prevent unnecessary addition reactions to the terminated solution, 1 g of hydroquinone was added and reacted for 6 hours. At the end of the reaction, washed with ethanol and dried.

Example 4: Flame Retardant Polymer Preparation

10 g of the mesh flame retardant prepared in Example 3 was dispersed in 100 g of a diamine-based material which is a polyurethane precursor. 10 g of flame retardant was added thereto, followed by stirring for 1 hour after sonication for 30 minutes. The dispersed solution was reacted with 100 g of an isocyanate-based material to prepare a flame retardant polyurethane.

In the above, the present invention has been described with reference to the above embodiments, which are only examples, and the present invention includes various modifications and other equivalent embodiments which are obvious to those skilled in the art. It should be understood that it can be carried out within the scope of the appended claims.

11 and 12: plate-like fillers (nano clay based materials and graphene based materials)
20: organic group
31 and 32: Organic Plated Fillers
40: polymerization initiator or catalyst
50: polymer matrix

Claims

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(a) binding the other end of the organic agent having an unsaturated bond at one end to the plate-shaped filler to obtain an organicated plate-shaped filler; And
(b) connecting the ends having unsaturated bonds of the organic plate-like filler with each other.

The method of claim 7, wherein
The plate-like filler is a nanoclay-based material;
The organicizing agent has a unsaturated bond at one end and phosphonium or imidazolium at the other end.

The method of claim 8,
The organicizing agent is a des-9-enyl triphenylphosphonium bromide, des-9-enyl-1,5-dimethylimidazolium, or a mixture thereof.

The method of claim 7, wherein
The plate-like filler is a graphene-based material;
The net flame retardant having an unsaturated bond at one end and a functional group selected from the group consisting of amide, amino, halogen, carboxyl, hydroxy, ester, ether, cyanate, and combinations thereof at the other end. Manufacturing method.

The method of claim 10,
Wherein said organicating agent is 18-vinyloctadecyl amide, 7-vinylheptanoyl chloride, cucurbic acid, N- (2-aminoethyl) maleimide, or a mixture thereof.

The method of claim 7, wherein
In the step (b), using azo-based polymerization initiator or Grubbs catalyst, the terminal having an unsaturated bond of the organic plate-like filler is connected to each other, a method of producing a flame retardant.

The method of claim 12,
The azo-based polymerization initiator is azobisisobutyronitrile (AIBN), 2,2'-azobis (4-methoxy-2,4-dimethyl valeronitrile), 2,2 ' -Azobis (2,4-dimethyl valeronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (N-butyl-2-methylpropionamide), and mixtures thereof;
Wherein said Grubbs catalyst is selected from the group consisting of primary Grubbs catalyst, secondary Grubbs catalyst, tertiary Grubbs catalyst, and mixtures thereof.

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