KR20200029129A - Flame retardant and flame retardant resin composition comprising the same - Google Patents

Abstract

The present invention relates to a flame retardant which is derived from a copolymer comprising a diene-based repeating unit and a vinyl aromatic repeating unit, and in which chlorine (Cl) is introduced into a double bond of the diene-based repeating unit, and to a flame-retardant resin composition comprising the same.

Description

Flame retardant and flame retardant resin composition comprising the same TECHNICAL FIELD FLAME RETARDANT AND FLAME RETARDANT RESIN COMPOSITION COMPRISING THE SAME

The present invention relates to a flame retardant and a flame retardant resin composition comprising the same.

Polymers are widely applied in various fields such as mechanical parts, office supplies, electronic devices, automobile industry, household appliances, or circuit boards. At this time, most of the polymers used are combustible and burn relatively easily. As described above, since the polymer is operated in a high temperature environment for a long time when applied to various electronic devices, the polymer needs to have excellent flame retardancy and thermal stability.

That is, in order to reduce or exclude the fire risk of the polymer in a high temperature environment, it is absolutely necessary to reduce the flammability and use a fire-resistant or heat-resistant resin composition.

Accordingly, a method in which a flame retardant is added to the polymer is generally used for the purpose of preventing ignition for a specific time or retarding the spread of fire significantly.

Among them, an aliphatic brominated flame retardant such as hexabromocyclododecane (HBCD), which has a high thermal stability, is known as a conventional flame retardant and has been used in flame retardant applications for expanded styrene.

However, flame retardants including HBCD have recently been found to disturb the hormonal system and have a detrimental effect on the human body, such as the nervous system and the immune system, and have become a cause of environmental pollution upon disposal, and are thus restricted for use.

In addition, although a method of using a phosphorus-based flame retardant is known, the phosphorus-based flame retardant is vulnerable to heat and generates a gas when injection molding a resin composition containing the same, or has a problem of lowering the heat resistance of the resin composition.

In addition, as another flame retardant, a metal hydroxide-based flame retardant has been proposed. However, the metal hydroxide-based flame retardant has a problem that not only sufficient flame retardancy is not obtained when not blended in a large amount, but also degrades the processability of the resin and the physical properties of the molded article.

Accordingly, there is a need for a flame retardant that has less harmful effects on the human body and is excellent in stability against heat such as high temperature, and has a more improved flame retardant effect in order to suppress combustion such as ignition of the resin composition.

One aspect of the present invention has an object to provide a flame retardant that can not only have excellent flame retardancy as a flame retardant per se, but also improve flame retardancy in a resin composition.

One aspect of the present invention is to provide a flame retardant that is excellent in thermal stability, and can prevent combustion even at high temperatures.

According to an aspect of the present invention, an object of the present invention is to provide a flame retardant resin composition having excellent miscibility with a resin and a flame retardant and improving flame retardancy and thermal stability.

The flame retardant according to the present invention is derived from a copolymer containing a diene-based repeating unit and a vinyl aromatic repeating unit, and chlorine (Cl) is introduced into the double bond of the diene-based repeating unit.

With respect to the total moles of the double bond according to an aspect of the present invention, chlorine (Cl) may be introduced in an amount of 15 to 100 mol%.

With respect to the total moles of the double bond according to an aspect of the present invention, chlorine (Cl) and bromine (Br) may be introduced at least 70 mol%.

With respect to the total moles of the double bond according to an aspect of the present invention, 65 to 90 mol% of chlorine (Cl) and 10 to 35 mol% of bromine (Br) may be introduced.

The copolymer according to an aspect of the present invention may be to introduce chlorine first to a double bond, and then to bromine.

The copolymer according to one aspect of the present invention may have a diene-based repeating unit content of 10 to 90 mol%.

The diene repeating unit according to an aspect of the present invention is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl It can be derived from any one or two or more monomers selected from -1,3-butadiene and the like.

The vinyl aromatic repeating unit according to an aspect of the present invention may be derived from any one or two or more monomers selected from styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene and p-tert-butylstyrene. have.

The copolymer according to an aspect of the present invention may be a block copolymer of a diene-based repeating unit and a vinyl aromatic repeating unit.

The flame retardant according to an aspect of the present invention may have a 5 wt% loss pyrolysis temperature (T _d ) measured by thermogravimetric analysis of 200 ° C or higher.

The flame retardant according to an aspect of the present invention may have a limiting oxygen index (LOI) of 22% or more.

The flame-retardant resin composition according to the present invention includes the above-mentioned flame retardant.

The flame-retardant resin composition according to an aspect of the present invention may contain 1 to 50 parts by weight of a flame retardant relative to 100 parts by weight of the resin.

The flame retardant according to an aspect of the present invention may have excellent flame retardancy as well as excellent thermal stability at high temperatures.

In addition, the flame-retardant resin composition according to an aspect of the present invention is excellent in the miscibility of the flame retardant and the resin as well as excellent flame retardancy and thermal stability to prevent ignition or to significantly delay the spread of fire.

1 is a schematic diagram showing a reaction process of a chlorine-containing flame retardant according to an embodiment of the present invention.
Figure 2 is a schematic diagram showing the reaction process of a flame retardant introduced with chlorine and bromine according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail. However, the following examples are only a reference for explaining the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is merely for effectively describing a specific embodiment, and is not intended to limit the present invention.

The present invention relates to a flame retardant and a flame retardant resin composition comprising the same.

The present invention will be described in detail as follows.

The flame retardant according to the present invention is derived from a copolymer containing a diene-based repeating unit and a vinyl aromatic repeating unit, and chlorine (Cl) is introduced into the double bond of the diene-based repeating unit.

The flame retardant according to the present invention is excellent in flame retardancy, and when mixed with a resin composition, can provide excellent flame retardancy to the resin composition. In addition to this, it is possible to stably impart flame retardancy even when used at high temperature with excellent thermal stability that does not cause thermal decomposition at high temperatures.

The flame retardant according to the present invention, by introducing chlorine (Cl) to the double bond, may have excellent flame retardancy as well as excellent thermal stability, and may have durability that does not decompose even at high temperatures. Preferably, the diene-based repeating unit may have 15 to 100 mol% of chlorine (Cl), more preferably 60 to 100 mol% of total moles of double bonds, and thus have more excellent flame retardancy and thermal stability, It can have durability that does not decompose even at high temperatures.

According to an aspect of the present invention, the flame retardant may be introduced into the double bond, chlorine and bromine.

Preferably, according to an aspect of the present invention, with respect to the total moles of the double bond, chlorine (Cl) and bromine (Br) may be introduced at least 70 mol%. Preferably, 80 mol% or more of chlorine (Cl) and bromine (Br) may be introduced based on the total moles of the double bond.

According to another aspect of the present invention, preferably, the total amount of the double bond, 65 to 90 mol% of chlorine (Cl) and 10 to 45 mol% of bromine (Br) may be introduced. More preferably, 70 to 85 mol% of chlorine (Cl) and 15 to 30 mol% of bromine (Br) may be introduced based on the total moles of the double bond.

When the copolymer containing chlorine and bromine is introduced as described above, not only does it maintain excellent flame retardancy compared to the copolymer in which only bromine is introduced, but also has a high thermal decomposition temperature and excellent thermal stability, so it is possible to prevent a risk that occurs during the combustion process. have. More preferably, both the chlorine and bromine relative to the total mole of the double bond, such as the copolymer introduced with respect to the total mole of the double bond, the latter chlorine (Cl) 65 to 90 mol% and bromine (Br) 10 to 45 mol% When substituted, it can provide more improved flame retardancy and thermal stability.

When a bromine-only copolymer is included, the bromine is highly volatile and dissociates at a significantly lower temperature than the flame retardant according to the present invention. In addition, during storage, bromine is easily detached due to low durability, and storage stability is not good, and thus additional processes or auxiliary agents are required.

On the other hand, the flame retardant according to the present invention is that by introducing chlorine, and having thermal stability even at a remarkably high temperature, it can have excellent flame retardancy and heat resistance at the same time. In addition, during storage, chlorine is not desorbed even at high temperature due to its excellent durability, and furthermore, it is possible to improve stability against bromine introduced together, and thus, storage stability is more excellent.

According to one aspect of the invention, the copolymer may have a diene-based repeating unit content of 10 to 90 mol%. Preferably, the content of the diene-based repeating unit may be 30 to 90 mol%. More preferably, the content of the diene-based repeating unit may be 50 to 90 mol%. When the content of the diene-based repeating unit is as described above, miscibility with the resin may be improved, and excellent flame retardancy and thermal stability may be provided.

According to an aspect of the present invention, the diene-based repeating unit is not particularly limited as long as it is a hydrocarbon repeating unit containing a double bond, but for example, 1,3-butadiene, 2,3-dimethyl-1,3- It can be derived from any one or more monomers selected from butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3-butadiene. By introducing chlorine into the double bond of the diene-based repeating unit as described above, a flame retardant having excellent flame retardancy and heat resistance can be provided. Moreover, by introducing chlorine and bromine together into the double bond of the diene-based repeating unit, it is possible to provide more excellent flame retardancy and heat resistance.

According to an aspect of the present invention, the copolymer may be to introduce chlorine into a diene-based repeating unit as shown in FIG. 1.

Preferably, the diene-based repeating unit is, for example, a repeat comprising 1,4-polybutadiene derived from 1,3-butadiene and having a double bond formed on the side chain, and 1,2-polybutadiene having a double bond formed on the main chain. It may be to include a unit. The flame retardant according to the present invention is capable of introducing chlorine to the double bond thus formed.

According to an aspect of the present invention, the copolymer may be to first introduce bromine to the double bond, and then to further introduce chlorine.

According to another embodiment, the copolymer may be to simultaneously introduce bromine and chlorine to the double bond.

According to another aspect, preferably, the copolymer may be to introduce chlorine first to a double bond, and then to further introduce bromine, as shown in FIG. 2.

Moreover, according to one aspect of the present invention, by going through an introduction process as shown in FIG. 2, the copolymer is first provided with chlorine to the double bonds of the side chains and some main chains, and the additionally introduced bromine is the residual doubles of the main chains. It may be a reaction to binding. In addition, the element located in the side chain is desorbed first at a high temperature, and chlorine dissociated at a high temperature is introduced into the side chain, thereby providing excellent flame retardancy and heat resistance, so that it can be more stable at higher temperatures. Since all chlorine is introduced, it has excellent thermal stability at high temperatures.

According to an aspect of the present invention, the vinyl aromatic repeating unit is not particularly limited, but the more excellent the miscibility with the aromatic resin composition, the more preferable. Specific examples may be derived from any one or more monomers selected from styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, and p-tert-butylstyrene. When the vinyl aromatic repeating unit is included, mechanical strength may be further improved, and durability and heat resistance may be further improved.

According to an aspect of the present invention, the copolymer may have a weight average molecular weight of 1,000 to 1,000,000 g / mol. Preferably, it may be 10,000 to 500,000 g / mol, but is not limited thereto. When having the weight average molecular weight as described above, it is possible to improve the mechanical properties, it can have excellent processability in the resin composition.

According to an aspect of the present invention, the copolymer may include a diene-based repeating unit and a vinyl aromatic-based repeating unit, a random copolymer or a block copolymer. Preferably, the copolymer is uniformly imparted flame retardancy and thermal stability, and may be a block copolymer in terms of ease of introduction of chlorine and bromine.

For a specific example, the copolymer is a styrene-butadiene block copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-styrene-butadiene block copolymer (SBSB), styrene-butadiene-styrene -Butadiene-styrene block copolymer (SBSBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butadiene-styrene block copolymer (SEBS) and styrene-butylene-butadiene-styrene block copolymer (SBBS It may be derived from a copolymer comprising any one or two or more selected from).

According to an aspect of the present invention, the flame retardant may be to perform a reaction for introducing chlorine and bromine into the copolymer at -70 ° C to 80 ° C. Preferably it may be to perform a reaction for introducing chlorine and bromine to the copolymer at -20 ℃ to 50 ℃. The flame retardant according to the present invention can easily introduce chlorine and bromine even at such low temperatures. In addition, when reacting at a high temperature, chlorine and bromine are introduced into the aromatic ring of the vinyl aromatic repeating unit instead of a double bond, and when chlorine or bromine is introduced into the aromatic ring, the properties of the copolymer change and the aromatic repeating unit is added. The miscibility with the containing resin may be lowered. In addition, by reacting at a low temperature, such a reaction can be suppressed and flame retardancy and thermal stability can be simultaneously improved. In addition, there is an advantage in designing equipment and processes as it is possible to manufacture at a low temperature, room temperature, and a wide reaction possible temperature up to 50 ° C.

According to an aspect of the present invention, the flame retardant may further include any one or two or more additives selected from flame retardant additives, flame retardant aids, heat stabilizers, ultraviolet stabilizers, nucleating agents, antioxidants, blowing agents, acid removers and colorants, etc. However, it is not limited thereto.

According to an aspect of the present invention, the flame retardant may have a 5 wt% lossy thermal decomposition temperature (T _d ) measured by thermogravimetric analysis of 200 ° C or higher. Preferably, the 5% by weight loss pyrolysis temperature (T _d ) measured by thermogravimetric analysis may be 230 ° C or higher. More preferably, the 5% by weight loss pyrolysis temperature (T _d ) measured by thermogravimetric analysis may be 250 ° C or higher.

Specifically, according to one aspect, the flame retardant has a 5% by weight loss pyrolysis temperature (T _d ) measured by thermogravimetric analysis at a heating rate of 10 ° C./min from room temperature to 700 ° C. under a nitrogen atmosphere at 210 to 350 ° C. You can. Preferably, the 5% by weight loss pyrolysis temperature (T _d ) may be 230 to 350 ° C. More preferably, the 5% by weight loss pyrolysis temperature (T _d ) may be 250 to 350 ° C.

Specifically, according to one aspect, the flame retardant has a 5 wt% lossy thermal decomposition temperature (T _d ) measured by thermogravimetric analysis at an elevated temperature of 10 ° C./min from room temperature to 700 ° C. under an air atmosphere at 210 to 350 ° C. You can. Preferably, the 5% by weight loss pyrolysis temperature (T _d ) may be 230 to 350 ° C. More preferably, the 5% by weight loss pyrolysis temperature (T _d ) may be 250 to 350 ° C.

When having the thermal decomposition temperature as described above, it is not easily dissociated even at high temperature, and thus excellent flame retardancy can be secured. Furthermore, by having a high thermal decomposition temperature even under an air atmosphere, it is possible to secure durability against combustion in real life with excellent thermal stability. have.

According to an aspect of the present invention, the flame retardant may have a limiting oxygen index (LOI) of 22% or more. Preferably, the flame retardant may have a limiting oxygen index (LOI) of 25% or more. More preferably, the flame retardant may have a limiting oxygen index (LOI) of 26% or more. Specifically, the flame retardant may have a limiting oxygen index (LOI) of 22 to 50%. Preferably, the flame retardant may have a limiting oxygen index (LOI) of 25 to 40%. More preferably, the flame retardant may have a limiting oxygen index (LOI) of 26 to 40%. When having the above-described limiting oxygen index, it means that the lowest concentration of oxygen required to continuously burn is higher than the concentration of oxygen in air, and thus has excellent flame retardancy. Such excellent flame retardancy can prevent ignition or significantly delay the spread of fire.

In another aspect of the present invention, there is provided a flame retardant resin composition comprising the above-described flame retardant.

The flame-retardant resin composition according to the present invention includes the above-described flame retardant, not only provides excellent flame retardancy, but also has excellent thermal stability, so that thermal decomposition does not occur at high temperatures, and thus can provide excellent flame retardancy in high temperature environments such as fire. .

According to an aspect of the present invention, the flame retardant resin composition may further include a resin in addition to the flame retardant.

According to an aspect of the present invention, the resin is not particularly limited, but may include a resin excellent in miscibility with the flame retardant described above.

Specifically, it may be a resin containing any one or two or more selected from vinyl aromatic polymers, olefin polymers and acrylic polymers. In addition, it may include a halogenated resin. Preferably, the flame retardant resin composition may include a vinyl aromatic polymer in terms of improving flame retardancy.

For a specific example, the resin is polyethylene, chlorinated polyethylene, polypropylene, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-ethylene-styrene copolymer, styrene-butylene-styrene Copolymers, styrene-propylene-styrene copolymers and styrene-propylene-styrene copolymers. Preferably polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-ethylene-styrene copolymer, styrene-butylene-styrene copolymer, styrene-propylene-styrene copolymer and styrene- It may include any one or two or more selected from propylene-styrene copolymer.

Flame-retardant resin composition according to the present invention, in accordance with one aspect, in terms of improving the compatibility between two or more poorly compatible resin, it is possible to improve compatibility by including two or more mixed resins with a flame retardant. Preferably, for example, by mixing polystyrene excellent in miscibility with respect to the vinyl aromatic repeating unit of the flame retardant according to the present invention or polyethylene or chlorinated polyethylene with good compatibility with respect to the diene repeating unit, compatibility is poor 2 Compatibility between species of resins can be improved. In addition, a flame retardant resin composition having significantly improved flame retardancy and thermal stability can be provided with such excellent compatibility.

According to an aspect of the present invention, the flame retardant resin composition may further include a compatibilizer to inhibit phase separation between the flame retardant and the resin. Moreover, in order to suppress the phase separation of the vinyl aromatic resin and the flame retardant, a phenolic compatibilizer may be further included. The phenol-based compatibilizer may be, for example, any one or two or more mixtures selected from BASF's IGANOX series and Songwon Industrial's SONGNOX series.

When further comprising a compatibilizer as described above, it is possible to provide a flame-retardant resin composition not only to suppress phase separation, but also to significantly improve flame retardancy and thermal stability.

According to an aspect of the present invention, the flame retardant resin composition may contain 1 to 50 parts by weight of a flame retardant relative to 100 parts by weight of the resin. Preferably, the flame retardant may contain 5 to 30 parts by weight based on 100 parts by weight of the resin. By including the flame retardant in the above content, it is possible not only to have excellent thermal stability that does not undergo thermal decomposition even at high temperatures, and to have excellent flame retardancy at the same time. In addition, during storage, chlorine is not desorbed due to its excellent durability, and further, the stability to bromine introduced together can be improved, and thus, storage stability is excellent.

As described above, although the embodiments of the present invention have been described in detail, a person having ordinary knowledge in the technical field to which the present invention pertains, the present invention without departing from the spirit and scope of the present invention as defined in the appended claims. The invention may be modified in various ways. Therefore, changes in the embodiments of the present invention will not be able to escape the technology of the present invention.

 [Method of measuring properties]

1. Pyrolysis temperature

The thermal decomposition temperature was measured by heating at a heating rate of 10 ° C / min from room temperature to 700 ° C under a nitrogen atmosphere or an air atmosphere through a thermogravimetric method (TGA, Q500). At this time, the thermal decomposition temperature was reduced by 5% by weight. The thermal decomposition temperature (T _d ) and the maximum thermal decomposition temperature (T _dmax ) were measured.

2. LOI (Limited Oxygen Index)

The limiting oxygen index was measured according to ASTM D2863, Type 4.

[Example 1]

After adding 500 parts by weight of chloroform to 100 parts by weight of styrene-butadiene-styrene block copolymer (74 mol% of butadiene content and 26 mol% of styrene content) in a 10 L polymerization reactor, 150 parts by weight of chlorine was injected through a mass flow controller at 20 ° C. The reaction was carried out for 4 hours. Thereafter, 200 parts by weight of bromine was injected to react at 20 ° C. for 4 hours to prepare a copolymer in which 80 mol% of chlorine and 20 mol% of bromine were introduced with respect to the total mol of butadiene. The prepared copolymer was precipitated in ethanol to obtain a solid in the form of a white powder, and the obtained flame retardant was measured through the above method for measuring physical properties.

 [Example 2]

In Example 1, with respect to the total mole of butadiene, a copolymer in which 75 mol% of chlorine and 25 mol% of bromine was introduced was prepared by injecting 140 parts by weight of chlorine and 250 parts by weight of bromine.

[Example 3]

In Example 1, with respect to the total mole of butadiene, 90 parts by weight of chlorine and 500 parts by weight of bromine were injected to prepare a copolymer in which 50 mol% of chlorine and 50 mol% of bromine were introduced.

[Example 4]

In Example 1, with respect to the total mole of butadiene, 50 parts by weight of chlorine and 750 parts by weight of bromine were injected to prepare a copolymer in which 25 mole% of chlorine and 75 mole% of bromine were introduced.

[Example 5]

In Example 1, with respect to the total mole% of butadiene, 170 parts by weight of chlorine and 100 parts by weight of bromine were injected to prepare a copolymer in which 90 mole% of chlorine and 10 mole% of bromine were introduced.

[Example 6]

In Example 1, with respect to the total mole of butadiene, a copolymer in which 100 mol% of chlorine was introduced was prepared by injecting 190 parts by weight of chlorine.

[Example 7]

In Example 1, with respect to the total mole of butadiene, a copolymer in which 80 mol% of chlorine was introduced was prepared by injecting 150 parts by weight of chlorine.

[Example 8]

In Example 1, 150 parts by weight of chlorine and 50 parts by weight of bromine were injected with respect to the total mole of butadiene to prepare a copolymer in which 80 mol% of chlorine and 5 mol% of bromine were introduced.

[Comparative Example 1]

After adding 500 parts by weight of chloroform to 100 parts by weight of styrene-butadiene-styrene block copolymer (74 mol% butadiene content, 26 mol% styrene content) in a 10 L polymerization reactor, 1000 parts by weight of bromine was injected through a mass flow controller at 20 ° C. By reacting for 4 hours, a copolymer in which 100 mol% of bromine was introduced relative to the total mol of butadiene was prepared. The prepared copolymer was precipitated in ethanol to obtain a solid in the form of a white powder, and the obtained flame retardant was measured through the above method for measuring physical properties.

The copolymers prepared in Examples 1 to 8 and Comparative Example 1 were uniformly mixed with 20 parts by weight of a polystyrene (weight average molecular weight of 150,000 g / mol) using a Henschel mixer, and then through a twin screw extruder. The hot press temperature was pressed at 150 ° C to prepare a flame-retardant resin composition in the form of a sheet. On the other hand, in Table 1 below, the limiting oxygen index was measured and shown. In addition, the thermal decomposition temperatures of the copolymers prepared in Examples 1 to 8 and Comparative Example 1 were measured and are shown in Table 1 below.

[Comparative Example 2]

With respect to 100 parts by weight of polystyrene (weight average molecular weight 150,000 g / mol), 20 parts by weight of hexabromocyclododecane was uniformly mixed using a Henschel mixer, and then pressurized by a hot press temperature of 150 ° C through a twin-screw extruder. A flame-retardant resin composition in the form of a sheet was prepared. The limiting oxygen index of the flame-retardant resin composition prepared in Comparative Example 2 was measured and is shown in Table 1 below.

5% by weight loss
Pyrolysis temperature (T _d ) Maximum pyrolysis temperature (T _dmax ) Marginal oxygen index (%) N ₂ Air N ₂ Air Example 1 300.8 272.8 457.5 387.2 27 Example 2 297.5 268.1 441.2 379.3 27 Example 3 221.5 210.3 429.3 372.4 25 Example 4 201.5 202.1 434.3 337.3 28 Example 5 305.7 286.2 460.1 392.9 25 Example 6 310.6 292.4 468.9 398.7 24 Example 7 241.0 239.2 452.0 332.0 22 Example 8 283.0 276.0 433.1 330.0 24 Comparative Example 1 221.1 222.5 233.4 238.4 28 Comparative Example 2 244.2 224.2 274.3 268.2 28

As shown in Table 1, the flame retardant according to the present invention has a high thermal stability by introducing chlorine, and has a high value of 5% by weight loss pyrolysis temperature, maximum pyrolysis temperature and limiting oxygen index, and only the bromine-introduced copolymer is introduced. Contrast, it was confirmed to maintain excellent flame retardancy.

In addition, it was confirmed that the flame retardant according to the present invention has excellent thermal stability by introducing chlorine and bromine, and maintains excellent flame retardancy compared to a copolymer in which only bromine is introduced.

Moreover, Examples 1 and 2, when compared to Examples 3 to 6, when compared to 65 to 90 mol% of chlorine (Cl) and 10 to 45 mol% of bromine (Br) introduced copolymer, more excellent thermal stability And it was confirmed that the flame retardancy can be secured. Moreover, when the copolymer containing 70 to 85 mol% of chlorine (Cl) and 15 to 30 mol% of bromine (Br) is introduced, based on the total mole of the double bond of the diene-based repeating unit, it is not only excellent in flame retardancy, but also at high temperature. Also, it was confirmed that the stability is excellent and the chlorine and bromine are prevented from being detached, thereby having excellent durability.

In addition, it was confirmed that Examples 1 and 2, when compared with Examples 7 to 8, when chlorine and bromine were introduced with respect to the total mole of double bonds, more excellent thermal stability and flame retardancy can be secured.

When a copolymer containing only bromine as in Comparative Example 1 was included, it was confirmed that, due to high volatility, it began to dissociate at a low temperature, resulting in poor durability, and significantly lower heat resistance than Example 1.

In addition, when preparing a flame retardant resin composition including a conventional flame retardant as in Comparative Example 2, some of the flame retardancy is secured, but its use is prohibited due to the toxicity of the material itself, and thermal stability is significantly reduced compared to Example 1 I could confirm that.

Therefore, the flame retardant according to the present invention can not only secure excellent flame retardancy, but also have a high thermal decomposition temperature, thereby ensuring excellent thermal stability and durability even at high temperatures. In addition, by having a high thermal decomposition temperature in an air atmosphere in addition to a nitrogen atmosphere, it is possible to secure excellent durability even in a high-temperature environment generated in real life.

As described above, in the present invention, a flame retardant and a flame retardant resin composition including the same have been described through specific matters and limited examples, which are provided only to help a more comprehensive understanding of the present invention, and the present invention It is not limited, and those skilled in the art to which the present invention pertains can make various modifications and variations from these descriptions.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and should not be determined, and all claims that are equivalent or equivalent to the scope of the claims as well as the claims to be described later belong to the scope of the spirit of the invention. .

Claims (13)

Derived from a copolymer comprising a diene-based repeating unit and a vinyl aromatic repeating unit,
A flame retardant in which chlorine (Cl) is introduced into a double bond of a diene-based repeating unit. According to claim 1,
A flame retardant, in which 15 to 100 mol% of chlorine (Cl) is introduced, based on the total amount of the double bonds. According to claim 1,
A flame retardant, in which chlorine (Cl) and bromine (Br) are introduced in an amount of 70 mol% or more based on the total amount of the double bonds. According to claim 3,
A flame retardant that is introduced with 65 to 90 mol% of chlorine (Cl) and 10 to 35 mol% of bromine (Br) relative to the total moles of the double bond. According to claim 4,
A flame retardant that introduces chlorine first into the double bond and then introduces bromine. According to claim 1,
The copolymer is a flame retardant having a diene-based repeating unit content of 10 to 90 mol%. According to claim 1,
The diene repeating units are 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3-butadiene. Flame retardant derived from any one or more monomers selected. According to claim 1,
The vinyl aromatic repeating unit is a flame retardant derived from any one or more monomers selected from styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene and p-tert-butylstyrene. According to claim 1,
The copolymer is a flame retardant which is a block copolymer of a diene-based repeating unit and a vinyl aromatic repeating unit. According to claim 1,
The flame retardant is a flame retardant having a 5 wt% loss pyrolysis temperature (T _d ) of 200 ° C. or higher measured by thermogravimetric analysis. According to claim 1,
The flame retardant has a limiting oxygen index (LOI) of at least 22%. Flame-retardant resin composition comprising the flame retardant of any one of claims 1 to 11. The method of claim 12,
The flame-retardant resin composition is a flame-retardant resin composition containing 1 to 50 parts by weight of a flame retardant relative to 100 parts by weight of the resin.

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