TW202146533A - Polymerization inhibitor for a polyarylene sulfide resin - Google Patents

Abstract

The present invention provides a polymerization inhibitor for a polyarylene sulfide resin, which comprises a compound having a specific structure, a polyarylene sulfide resin composition comprising the same, a process for preparing a polyarylene sulfide resin using the same, and a polyarylene sulfide resin prepared using the same. According to the present invention, it is possible to reduce the formation of a side-chain structure in the polyarylene sulfide resin, thereby improving the linearity, and to enhance the mechanical properties and processing stability.

Description

Polymerization inhibitor for polyarylene sulfide resin

The present invention relates to a polymerization inhibitor for polyarylene sulfide resin containing a compound having a specific structure; a polyarylene sulfide resin composition containing the polymerization inhibitor; a preparation of polyarylene sulfide using the polymerization inhibitor A method of resin; and a polyarylene sulfide resin prepared using the polymerization inhibitor.

Background of the Invention

Polyarylene sulfide is an important engineering plastic. Its properties, such as high heat resistance, high chemical resistance, non-flammability, and high strength, have continuously increased its demand for various uses such as high-durability plastic molded products and electrical products.

Polyphenylene sulfide is the only polyarylene sulfide currently sold on a commercial scale. Representative methods for producing it are a solution polymerization method in which p-dichlorobenzene and sodium sulfide are polymerized as raw materials in an N-methylpyrrolidone solvent; and a melt polymerization method in which a diiodoaromatic compound and a sulfur compound are used as raw materials. The raw materials are polymerized at high temperature without the use of solvents.

However, it is known that the heat resistance, flame resistance and durability of polyphenylene sulfide resins produced by solution polymerization are adversely affected by a large amount of outgassing due to the use of solvents and chlorine contained in the raw materials.

In contrast, the polyphenylene sulfide resin produced by the melt polymerization method produces an improvement effect, because it does not use a solvent, the polyphenylene sulfide resin has an excellent productivity and cost structure, has a small amount of outgassing, and because It has excellent corrosion resistance without using chlorine-based raw materials.

At the same time, in the process of manufacturing and/or processing polyarylene sulfide, polymerization inhibitors, such as Diphenyl disulfide and mercaptobenzothiazole (see Korean Patent No. 1,944,898).

The present inventors have found that although the polyarylene sulfide resin prepared by the melt polymerization method produces an improvement effect compared to the polyarylene sulfide resin prepared by the solution polymerization method as described above, there is a linearity due to the general process. This problem results in poor mechanical strength in terms of tensile strength and impact strength, and may not have sufficient elongation when used in applications as fibers and films.

As a result of extensive research conducted under this background, the present inventors have found that the above-mentioned problems can be solved by changing the polymerization inhibitor of the polyarylene sulfide resin, thereby completing the present invention. [Prior Art Literature] [Patent Literature] (Patent Document 1) Korean Patent No. 1,944,898

technical problem

The present invention aims to provide a novel polymerization inhibitor for polyarylene sulfide resin; a method for preparing polyarylene sulfide resin using the polymerization inhibitor; and a polyarylene sulfide resin prepared using the polymerization inhibitor. problem solution

According to an embodiment of the present invention, a polymerization inhibitor for polyarylene sulfide resin is provided, wherein the polymerization inhibitor includes a compound having a specific structure.

According to another embodiment of the present invention, a polyarylene sulfide resin composition is provided, and the polyarylene sulfide resin composition includes a diiodo aromatic compound, a sulfur compound and the above polymerization inhibitors.

According to another embodiment of the present invention, there is provided a method for preparing a polyarylene sulfide resin, the method comprising melt polymerizing a composition comprising a diiodo aromatic compound, a sulfur compound and the above polymerization inhibitor.

According to another embodiment of the present invention, there is provided a polyarylene sulfide resin prepared by melt-polymerizing a composition comprising a diiodo aromatic compound, a sulfur compound and the above polymerization inhibitor. Advantageous Effects of the Invention

When the polymerization inhibitor used in the polyarylene sulfide resin of the examples is used to prepare the polyarylene sulfide resin, its linearity can be enhanced by reducing the formation of side chain structures in the polyarylene sulfide resin, thereby improving the Mechanical properties of the finally obtained polyarylene sulfide resin, such as strength and elongation.

Best Mode for Carrying out the Invention

Hereinafter, the present invention is described in detail.

The embodiments are not limited to those described below. Specifically, it can be modified into various forms as long as the gist of the present invention is not changed. [ Polymerization inhibitor for polyarylene sulfide resin ]

One embodiment relates to a polymerization inhibitor for polyarylene sulfide resin, which includes a compound having a specific structure.

The polyarylene sulfide resin can be prepared by solution polymerization of p-dichlorobenzene and sodium sulfide. Alternatively, it can be prepared by melt polymerization of a diiodoaromatic compound and a sulfur compound.

The polymerization inhibitor used for the polyarylene sulfide resin refers to a compound capable of terminating/inhibiting the polymerization reaction of the polyarylene sulfide resin. Specifically, the polymerization inhibitor may be a compound that terminates/inhibits polymerization by removing halogen groups contained in the polyarylene sulfide resin to be polymerized.

The polymerization inhibitor used in the polyarylene sulfide resin of the examples may contain a compound having a specific structure. Such a polymerization inhibitor may have an iodine group or a thioether bond in order to react with the polyarylene sulfide resin. Since the iodine group and the sulfide bond are reactive groups used in the polymerization of the polyarylene sulfide resin, the reaction can be carried out with a similar amount of reaction heat in the reactor, and the kind of by-products formed will be The same, so that it has excellent advantages in terms of process.

The polymerization inhibitor used for the polyarylene sulfide resin of the examples may contain a compound represented by the following formula 1. [Formula 1]

X ¹ and X ² are each independently selected from the group consisting of hydrogen, halo, alkyl having 1 to 3 carbon atoms, -OA ¹ , -SA ² , -COOA ^{3 , -NA 4} A ⁵ , -SO ₃ A ⁶ and -NHCOA ⁷ , Z ¹ to Z ⁴ are each independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl having 1 or 2 carbon atoms and having 1 or 2 carbon atoms A substituted or unsubstituted alkenyl group of carbon atoms, and p ¹ and p ² are each independently 1 or 2, wherein when Z ¹ and Z ² are alkenyl groups having 2 carbon atoms and are bonded to two adjacent when carbon atoms, which can be connected to each other to form a benzene ring, when Z ³ and Z ⁴ is an alkenyl group having 2 carbon atoms and is bonded to two adjacent carbon atoms, which can be connected to each other to form a benzene ring , and A ¹ to A ⁷ are each independently selected from the group consisting of hydrogen radicals, sodium cations, lithium cations, substituted or unsubstituted alkyl groups having 1 to 3 carbon atoms, substituted or unsubstituted benzene and substituted or unsubstituted naphthyl, wherein ^{the substituted alkyl group having 1 to 3 carbon atoms of A 1} to A ⁷ , the substituted phenyl group and the substituted naphthyl group each independently have a group selected from sulfur Substituents of the group consisting of alcohol group and phenyl sulfide group, the substituted alkyl group with 1 or 2 carbon atoms and the substituted alkenyl group with 1 or 2 carbon atoms of ^{Z 1} to Z ^{4 are each independently} has a substituent selected from the group consisting of halogen, hydroxyl, thiol, carboxyl, amine and sulfonic acid, and when X ¹ and X ² are both hydrogen atoms, Z ¹ and Z ² and Z ³ and Z ⁴ in the form of at least one substituted or unsubstituted benzene ring.

In particular, in the compound represented by Formula 1 ^{, at least one of Z 1} and Z ² and Z ³ and Z ⁴ can form a substituted or unsubstituted benzene ring, and/or one of X ¹ and X ² At least one can be selected from the group consisting of -OA ¹ , -SA ² , ^{-COOA 3} , -NA ⁴ A ⁵ , -SO ₃ A ⁶ and -NHCOA ⁷ , and A ¹ to A ⁷ can be independently selected from each other The group consisting of substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl.

In addition, in the compound represented by formula 1, Z ¹ and Z ² and Z ³ and Z ⁴ may form a substituted or unsubstituted benzene ring, and/or X ¹ and X ² may be selected from the group consisting of:- OA ¹ , -SA ² , ^{-COOA 3} , -NA ⁴ A ⁵ , -SO ₃ A ⁶ and -NHCOA ⁷ , and A ¹ to A ⁷ may each be independently selected from substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl group.

In addition, the compound represented by Formula 1 may be a compound in which at least one of ^{X 1} and X ^{2 is -OA 1} , -SA ₂ , -COOA ^{3 , -NA 4} A ⁵ , -SO ³ A ₆ or - NHCOA ₇ , and/or ^{at least one of Z 1} to Z ⁴ is an alkyl or alkenyl group having 1 or 2 carbon atoms, and the alkyl or alkenyl group has a substituent selected from the group consisting of: halogen group, hydroxyl group (-OH), thiol group (-SH), carboxyl group (-COOH), amine group (-NH ² ) and sulfonic acid group (-SO ³ H). In this case, the compound represented by Formula 1 has a polar functional group, and the polyarylene sulfide resin prepared using the compound has a corresponding polar functional group, so that it will have enhanced compatibility with other resins or additives, thereby Produces excellent mechanical properties when blended with these other resins or additives.

The compound represented by Formula 1 generally has a disulfide bond, which is a reactive group capable of reacting with a polyarylene sulfide resin, so that the compound can be used as a polymerization inhibitor. In addition, since the compound has a core structure similar to the repeating unit of the polyarylene sulfide resin, the regularity of the chain of the polyarylene sulfide resin can be maintained, thereby minimizing the decrease in crystallinity that may be caused by the polymerization inhibitor.

In addition, while not being bound by any particular theory, because the compound represented by Formula 1 has a large molecular weight, it can be prevented from discharging the compound to the reaction during the decompression step in the preparation and/or processing of the polyarylene sulfide resin. The problem of the outside of the device is eliminated, thereby enhancing the linearity of the finally obtained polyarylene sulfide resin.

Specifically, when the polyarylene sulfide resin is prepared by melt polymerization, iodine is formed as a by-product from the diiodo aromatic compound and the like used as a raw material. Because iodine can generate free radicals and is highly reactive, unless it is properly removed, it may cause side reactions, such as the formation of side chain structures in polyarylene sulfide, thereby reducing the linearity of the polyarylene sulfide . The preparation process is carried out in a reduced pressure process in order to reduce such side reactions. The polymerization inhibitor may be discharged to the outside of the reactor during the decompression process, which may adversely affect the physical properties and processability of the polyarylene sulfide.

However, if the compound represented by Chemical Formula 1 having a large molecular weight is used as a polymerization inhibitor, the emission of the polymerization inhibitor is suppressed, which improves the efficiency of iodine removal and suppresses the formation of a side chain structure in polyarylene sulfide, by This can enhance the mechanical properties of polyarylene sulfide. In addition, the problems of mechanical corrosion caused by iodine remaining in the polyarylene sulfide during subsequent processing of the polyarylene sulfide and deterioration of processing stability due to an increase in the resin viscosity can be solved.

From this point of view, in the compound represented by Formula 1, the compound having a naphthalene structure bonded to a disulfide functional group or a phenyl group wherein the phenyl bonded to a disulfide functional group has -OA ¹ , -SA ² , Those compounds in which -COOA ^{3 , -NA 4} A ⁵ , -SO ₃ A ⁶ or -NHCOA ^{7 are} used as substituents (with the limitation that A ¹ to A ⁷ are phenyl or naphthyl) are particularly preferred.

Therefore, if the compound represented by Formula 1 is used to prepare and/or process a polyarylene sulfide resin, the formation of side chain structures in the polyarylene sulfide resin can be reduced and the amount of iodine remaining in the polyarylene sulfide resin can be reduced , so that processing stability can be improved while enhancing the mechanical properties of the final polyarylene sulfide resin.

Meanwhile, the compound represented by Chemical Formula 1 may have various functional groups depending on the application of the polyarylene sulfide resin prepared using the compound. Polyarylene sulfide resins are used for various purposes due to their excellent heat resistance. In particular, it can be used for electric vehicle parts, industrial pipes, coating resins, various films, fibers, and the like that require excellent heat resistance and rigidity. Here, the polyarylene sulfide resin is generally used in combination with other resins or additives having appropriate physical properties depending on the intended use. The preferred functional groups of the compound represented by Formula 1 may vary depending on the composition of these other resins or additives.

For example, non-polar end groups such as phenyl and naphthyl may be preferred when they are used in electronics with low halogen content. Polar end groups such as carboxyl, hydroxyl, amine and thiol groups may be preferred when mixed with other resins containing epoxy rings.

The polymerization inhibitor used for the polyarylene sulfide resin of the examples may contain a compound represented by the following formula 2. [Formula 2]

R ¹ to R ⁴ are each independently selected from the group consisting of hydrogen, halo, substituted or unsubstituted alkyl having 1 to 5 carbon atoms, -OA ⁸ , -SA ⁹ , -COOA ¹⁰ , -NA ¹¹ A ¹² , -SO ₃ A ¹³ and -NHCOA ¹⁴ , wherein A ⁸ to A ¹⁴ are each independently selected from the group consisting of hydrogen radicals, sodium cations, lithium cations, and hydroxyl radicals having 1 to 3 carbon atoms A substituted or unsubstituted alkyl group, and the substituted alkyl group with 1 to 5 carbon atoms in ^{R 1} to R ⁴ and the substituted alkyl group with 1 to 3 carbon atoms in ^{A 8} to A ¹⁴ Each independently has a thiol group as a substituent.

Additionally, ^{at least one of R 1} to R ⁴ may be a substituted alkyl group having 1 to 5 carbon atoms, or ^{at least one of R 1} to R ⁴ may be selected from the group consisting of -OA ⁸ , -SA ⁹ , ^{-COOA 10} , -NA ¹¹ A ¹² , -SO ₃ A ¹³ and -NHCOA ¹⁴ , and A ⁸ to A ¹⁴ may be substituted alkyl groups having 1 to 3 carbon atoms.

In addition, in the compound represented by Formula 2, R ¹ to R ⁴ may each be independently selected from the group consisting of a hydrogen group, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and -OA ⁸ , A ⁸ can each be independently selected from the group consisting of: hydrogen group, sodium cation, lithium cation and alkyl group with 1 to 3 carbon atoms, and R ¹ to R ⁴ have 1 to 5 carbon atoms in the group The substituted alkyl groups may each independently have a thiol group as a substituent.

In addition, in the compound represented by Formula 2, at least one of ^{R 1} to R ^{4 may be -OA 8} , -SA ⁹ , -COOA ^{10 , -NA 11} A ¹² , -SO ₃ A ¹³ or -NHCOA ¹⁴ . In this case, since the compound represented by Formula 2 has a polar functional group, the polyarylene sulfide prepared using the compound can be enhanced in mechanical properties when blended.

Since the compound represented by Formula 2 has a large number of functional groups, it can have a large molecular weight. Therefore, the problem of discharge to the outside of the reactor during the decompression process in the preparation and/or processing of the polyarylene sulfide resin can be prevented, thereby improving the efficiency of iodine removal and reducing the amount of iodine in the final polyarylene sulfide resin. iodine content. In addition, since a plurality of functional groups are appropriately selected depending on the use of the polyarylene sulfide, it may be preferable when excellent compatibility is required. For example, the compound represented by Formula 2 may be particularly preferred when stronger bond strength with inorganic fillers is required.

In addition, when the compound represented by Formula 2 has an aliphatic functional group, it usually exists in a liquid state. Therefore, it has the great advantage that it can be introduced more easily than solid aromatic compounds.

The polymerization inhibitor used for the polyarylene sulfide resin of the Examples may contain a compound represented by the following formula 3. [Formula 3]

X ⁷ to X ¹² are each independently selected from the group consisting of hydrogen, halogen, alkyl having 1 to 5 carbon atoms, -OA ¹⁵ , -SA ¹⁶ , -COOA ^{17 , -NA 18} A ¹⁹ , -SO ₃ A ²⁰ and -NHCOA ²¹ , and R ⁵ and R ⁶ are each independently an alkylene group having 1 to 5 carbon atoms, wherein A ¹⁵ to A ²¹ are each independently selected from the group consisting of: hydrogen , sodium cations, lithium cations, and substituted or unsubstituted alkyl groups having 1 to 5 carbon atoms, wherein the substituted alkyl groups having 1 to 5 carbon atoms in A ¹⁵ to A ²¹ each independently have sulfur Alcohol group as a substituent.

Specifically, in the compound represented by Formula 3, X ⁷ to X ¹² may be -OA ¹⁵ , and A ¹⁵ may each be independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and a group having 1 to Substituted or unsubstituted alkyl of 5 carbon atoms.

In addition, in the compound represented by Formula 3, at least one of ^{X 7} to X ^{12 may be -OA 15} , -SA ¹⁶ , -COOA ^{17 , -NA 18} A ¹⁹ , -SO ₃ A ²⁰ or -NHCOA ²¹ . In this case, since the compound represented by Formula 3 has a polar functional group, the polyarylene sulfide prepared using the compound can be enhanced in mechanical properties when blended.

Although not bound by any particular theory, because the compound represented by Formula 3 has a large number of functional groups, it can have a large molecular weight, like the compound represented by Formula 2. Therefore, the problem of discharge to the outside of the reactor during the decompression process in the preparation and/or processing of the polyarylene sulfide resin can be prevented, thereby improving the efficiency of iodine removal and reducing the amount of iodine in the final polyarylene sulfide resin. iodine content. In addition, since a plurality of functional groups are appropriately selected depending on the use of the polyarylene sulfide, it may be preferable when excellent compatibility is required.

In addition, when the compound represented by Formula 3 has an aliphatic functional group, it usually exists in a liquid state. Therefore, it has the great advantage that it can be introduced more easily than solid aromatic compounds.

The polymerization inhibitor used for the polyarylene sulfide resin of the examples may contain a compound represented by the following formula 4. [Formula 4]

X ^{13 is} each independently selected from the group consisting of hydrogen, halo, alkyl having 1 to 5 carbon atoms, OA ²² , -SA ²³ , -COOA ^{24 , -NA 25} A ²⁶ , -SO ₃ A ²⁷ and -NHCOA ²⁸ , Z ⁵ and Z ⁶ are each independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl having 1 or 2 carbon atoms, and substituted or unsubstituted alkyl having 1 or 2 carbon atoms substituted or unsubstituted alkenyl, w is halo, and q is each independently an integer from 1 to 3, wherein when Z ⁵ and Z ⁶ are alkenyl groups having 2 carbon atoms and are bonded to two adjacent carbons atoms, which can be attached to each other to form a benzene ring, A ²² , A ²⁴ and A ²⁵ are each independently selected from the group consisting of sodium cations, lithium cations, substituted or unsubstituted cations having 1 to 5 carbon atoms substituted alkyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl, and A ²³ and A ²⁶ to A ²⁸ are each independently selected from the group consisting of hydrogen, sodium cation, lithium cation, Substituted or unsubstituted alkyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl having 1 to 5 carbon atoms ^{, wherein A 22} to A ^{28 have 1 to 5 carbon atoms} The substituted alkyl group, the substituted phenyl group and the substituted naphthyl group each independently have a substituent selected from the group consisting of thiol and phenyl thioether groups, and the substituted groups of Z ⁵ and Z ⁶ have 1 or 2 The substituted alkyl of 1 or 2 carbon atoms and the substituted alkenyl of 1 or 2 carbon atoms each independently have a substituent selected from the group consisting of halo, hydroxy, thiol, carboxyl, amine, and sulfonic acid group.

Specifically, in the compound represented by Formula 4, when q is 2 or more, ^{at least one of X 13} can be selected from the group consisting of: an alkyl group having 1 to 5 carbon atoms, -OA ²² , -SA ²³ , ^{-COOA 24} , -NA ²⁵ A ²⁶ , -SO ₃ A ²⁷ and -NHCOA ²⁸ . The compound represented by Formula 4 is a compound having substantially a halogen group. Although it is not bound by any particular theory, the sulfur groups derived from the disulfide bonds of the polyarylene sulfide resin react with the halogen groups contained in the compound represented by Formula 4 during the reaction, thereby reducing the final polyarylene sulfide The fraction of disulfide bonds in ether resins. Meanwhile, disulfide bonds in the polyarylene sulfide resin may be cleaved to generate sulfur groups, and the thus generated sulfur groups may cause side reactions, such as bonding with side chains of the polyarylene sulfide resin. Therefore, the compound represented by Formula 4 can reduce such side reactions to suppress the formation of side chain structures in the polyarylene sulfide resin, thereby enhancing the mechanical properties of the final resin and improving processing stability.

In addition, in the compound represented by Formula 4, X ¹³ may be selected from the group consisting of halo, -OA ²² , -SA ²³ , -COOA ^{24 , -NA 25} A ²⁶ , -SO ₃ A ²⁷ and -NHCOA ²⁸ . In this case, since the compound represented by Formula 4 has a polar functional group, the polyarylene sulfide prepared using the compound can be enhanced in its compatibility, thereby having improved mechanical properties when blended.

Specifically, when the compound represented by Formula 4 has -SA ²³ as X ¹³ , a structure similar to the monomer structure of polyarylene sulfide can be achieved. Therefore, it is especially preferred to have the advantage of minimizing the inhibition of crystallinity of the final resin.

The compound represented by any one of formulae 1 to 4 is commercially available, or one skilled in the art can synthesize the compound based on technical common sense.

More specifically, the polymerization inhibitor used for the polyarylene sulfide resin of the examples may contain the following compounds (1) to (31). (1) 1-(Naphthalene-2-yl)-2-(naphthalene-2-yl)disulfane (2) 1-(Naphthalene-1-yl)-2-(naphthalene-1-yl)disulfane (3) 1-(Naphthalene-1-yl)-2-(naphthalene-2-yl)disulfane (4) 1-(Naphthalene-1-yl)-2-benzenedisulfane (5) 1,2-bis(2-iodonaphthalen-6-yl)disulfane (6) 1,2-bis(1-iodonaphthalen-5-yl)disulfane (7) 1-(1-iodonaphthalen-5-yl)-2-(2-iodonaphthalene-6-yl)disulfane (8) 1-(1-iodonaphthalen-5-yl)-2-(4-iodophenyl)disulfane (9) 1,2-bis(2-carboxynaphthalen-6-yl)disulfane (10) 1,2-bis(2-hydroxynaphthalen-6-yl)disulfane (11) 1,2-bis(2-aminonaphthalen-6-yl)disulfane (12) 1,2-bis(2-mercaptonaphthalen-6-yl)disulfane (13) 1,2-bis(1-carboxynaphthalen-4-yl)disulfane (14) 4-(2-(1-Hydroxynaphthalen-4-yl)disulfanyl)naphthalene-1-carboxylic acid (15) 4-(2-(1-Hydroxynaphthalen-2-yl)disulfanyl)naphthalene-1-ol (16) 5-(2-(2-Hydroxynaphthalen-6-yl)disulfanyl)naphthalene-1-ol (17) 3-(Triethoxysilyl)propane-1-thiol (18) 3-(Trimethoxysilyl)propane-1-thiol (19) 3-(Hydroxydimethoxysilyl)propane-1-thiol (20) 3-(Trihydroxysilyl)propane-1-thiol (21) 3-(Dihydroxysilyl)propane-1-thiol (22) 1,2-bis(3-(triethoxysilyl)propyl)disulfane (23) 1,2-Bis(3-(trihydroxysilyl)propyl)disulfane (24) 1,2-Bis(3-(trimethoxysilyl)propyl)disulfane (25) 1-(3-(Triethoxysilyl)propyl)-2-(3-(trihydroxysilyl)propyl)disulfane (26) 4-Iodothiophenol (27) 1-ethoxy-4-iodobenzene (28) Ethyl(4-iodophenyl)sulfane (29) 1,2-bis(2-benzylaminophenyl-1-yl)disulfane (30) 1,2-Bis(2-naphtholin-1-yl)disulfane (31) 1,2-bis(2-(4-(phenylthio)benzylamino)phenyl-1-yl)disulfane

(17)

(2)

(18)

(3)

(19)

(4)

(20)

(5)

(21)

(6)

(22)

(7)

(23)

(8)

(24)

(9)

(25)

(10)

(26)

(11)

(27)

(12)

(28)

(13)

(29)

(14)

(30)

(15)

(31)

(16)

  [ 包含聚合抑制劑之聚芳硫醚樹脂組成物 ] The structures of compounds (1) to (31) are shown in Table 1 below. [Table 1] Numbering Compound structure Numbering Compound structure (1)

(17)

(2)

(18)

(3)

(19)

(4)

(20)

(5)

(twenty one)

(6)

(twenty two)

(7)

(twenty three)

(8)

(twenty four)

(9)

(25)

(10)

(26)

(11)

(27)

(12)

(28)

(13)

(29)

(14)

(30)

(15)

(31)

(16)

[ Polyarylene sulfide resin composition containing polymerization inhibitor ]

Another embodiment relates to a polyarylene sulfide resin composition comprising a diiodo aromatic compound, a sulfur compound and a polymerization inhibitor for the polyarylene sulfide resin.

Polymerization inhibitors for polyarylene sulfide resins are as described above.

The diiodo aromatic compound may be at least one selected from the group consisting of diiodobenzene, diiodonaphthalene, diiodobiphenyl, diiodobisphenol, and diiodobenzophenone, but is not limited thereto. In addition, among the above-mentioned compounds, the diiodoaromatic compound may have a substituent such as an alkyl group or a thiol group, or a diiodoaromatic compound in which an atom such as oxygen or nitrogen is contained in the aromatic group may also be used . In addition, diiodoaromatic compounds have various isomers, depending on where the iodine atom is attached. Among these isomers compounds in which the iodine is attached to the para position, such as p-diiodobenzene, 2,6-diiodonaphthalene or p,p'-diiodobiphenyl, may be more suitable.

The sulfur compound reacted with the diiodo aromatic compound is not particularly limited. The sulfur compound may be elemental sulfur. Typically, elemental sulfur exists at room temperature in the form of cyclooctasulfide (S ₈ ), in which eight atoms are linked. If sulfur is commercially available in any solid or liquid form other than the above, it can be used without limitation.

The polymerization inhibitor may be contained in an amount of 0.00001 to 5% by weight based on the total weight of the composition. Specifically, the polymerization inhibitor may be contained in an amount of 0.0001 to 4 wt %, 0.001 to 3 wt %, 0.01 to 2 wt %, or 0.1 to 1 wt % based on the total weight of the composition. [ Method for producing polyarylene sulfide resin using polymerization inhibitor ]

Another embodiment relates to a method for preparing a polyarylene sulfide resin, the method comprising melt polymerizing a composition comprising a diiodo aromatic compound, a sulfur compound, and a polymerization inhibitor for the polyarylene sulfide resin.

Diiodo aromatic compounds, sulfur compounds, and polymerization inhibitors for polyarylene sulfide resins are as described above.

The conditions used for the melt polymerization step are not limited as long as the temperature is high enough to allow the diiodo aromatic compound and the sulfur compound to polymerize. However, the melt polymerization step is preferably carried out under reduced pressure in order to remove iodine formed as a by-product. That is, the melt polymerization step can be performed under conditions of high temperature and reduced pressure. In particular, the melt polymerization step can be carried out at a temperature of 180 to 400°C. More specifically, the temperature of the melt polymerization step can be gradually increased from the initial reaction conditions to the final reaction conditions. For example, the initial reaction conditions may be 180 to 260°C, 190 to 250°C, or 200 to 240°C, and the final reaction conditions may be 270 to 350°C, 280 to 340°C, 290 to 330°C, or 300 to 320°C. In this case, the temperature increase rate may be 0.16 to 0.93°C/min, preferably 0.26 to 0.33°C/min.

Additionally, the melt polymerization step can be carried out at a pressure of 0.001 to 500 Torr. More specifically, the pressure of the melt polymerization step can be gradually reduced from initial reaction conditions to final reaction conditions. For example, the initial reaction conditions may be 10 to 500 Torr, 50 to 400 Torr, or 100 to 300 Torr, and the final reaction conditions may be 0.1 to 50 Torr, 0.3 to 30 Torr, or 0.1 to 10 Torr, specifically 0.1 to 5 Torr . In this case, the pressure reduction rate may be 0.93 to 4.65 Torr/min, preferably 1.33 Torr/min to 2.67 Torr/min.

The polymerization inhibitor may be included in the melt polymerization step in an amount of 0.00001 to 5% by weight, based on the total weight of the composition. Specifically, the polymerization inhibitor may be contained in an amount of 0.0001 to 4 wt %, 0.001 to 3 wt %, 0.01 to 2 wt %, or 0.1 to 1 wt % based on the total weight of the composition.

If the polymerization inhibitor includes a compound represented by one of Formula 1 to Formula 4 having a polar functional group, the polymerization inhibitor can act as both a polymerization inhibitor and a compatibilizer. Therefore, there is an advantage in that the process is simplified since the step of applying a separate compatibilizer to the polyarylene sulfide resin is not required. Meanwhile, because the step of applying a compatibilizer is usually performed at a higher temperature and a stronger shear stress than the polymerization step, the main chain of the polyarylene sulfide can be thermally decomposed. However, the use of a polymerization inhibitor with polar functional groups has another advantage in that it can overcome the problems that arise during the step of applying the compatibilizer.

In the melt polymerization step, the polymerization inhibitor may be added together with the diiodo aromatic compound and the sulfur compound in the initial stage of the reaction. Alternatively, it may be added after some of the compositions comprising the diiodo aromatic compound and the sulfur compound have been melt polymerized. Specifically, when the residual iodine content in the composition comprising the diiodo aromatic compound and the sulfur compound is 0.01 to 80% by weight, 5 to 80% by weight, 10 to 80% by weight, 50 to 80% by weight, 0.01 to 71% by weight % by weight, 5 to 71% by weight, 10 to 71% by weight, 50 to 71% by weight, 1 to 50% by weight, 1 to 20% by weight, 1 to 10% by weight, or 5 to 10% by weight, polymerization inhibition may be added agent.

If a polymerization inhibitor is added when the residual iodine content in the composition containing the diiodoaromatic compound and the sulfur compound is within the above content range, the disulfide bond ratio and the iodine content in the final polyarylene sulfide resin can be significantly reduced , so that mechanical properties and processing stability can be improved, or linearity can be significantly enhanced. [ Polyarylene sulfide resin prepared using polymerization inhibitor ]

Another embodiment relates to a polyarylene sulfide resin prepared by melt polymerizing a composition comprising a diiodo aromatic compound, a sulfur compound, and a polymerization inhibitor for the polyarylene sulfide resin.

The fraction of disulfide bonds in the polyarylene sulfide resin may be less than 0.27% by weight. Specifically, it may be 0.26 wt% or less, 0.25 wt% or less, 0.001 to 0.25 wt%, 0.01 to 0.25 wt%, 0.01 to 0.24 wt%, 0.01 to 0.23 wt%, 0.01 to 0.22 wt% , 0.01 to 0.21 wt % or 0.01 to 0.20 wt %.

The polyarylene sulfide prepared using the polymerization inhibitor has a lower fraction of disulfide bonds, so that the formation of a side chain structure in the polyarylene sulfide resin can be suppressed. In addition, since the disulfide bonds act as a brittle structure in the resin, the polyarylene sulfide having a reduced fraction of the disulfide bonds can be improved in heat resistance and mechanical properties.

In addition, the polyarylene sulfide resin may have a branch ratio greater than 0.58. The branching ratio is the alpha value calculated by the Mark Howink equation. The closer the value is to 1, the more linear the polymer is. The closer the value is to 0, the higher the degree of polymer branching. Specifically, the polyarylene sulfide resin may have a branching ratio of 0.59 to 1.0, 0.6 to 1.0, 0.6 to 0.9, 0.6 to 0.8, 0.6 to 0.75, or 0.6 to 0.7.

When the polyarylene sulfide resin is prepared using the polymerization inhibitor, the emission of the polymerization inhibitor is suppressed in the decompression step during the production of the polyarylene sulfide resin, thereby improving the removal efficiency of iodine or reducing the polyarylene sulfide during the reaction The fraction of disulfide bonds in the resin. Therefore, the formation of a side chain structure in the polyarylene sulfide resin can be suppressed, thereby increasing the branching ratio.

Additionally, the polyarylene sulfide resin may have an iodine content of less than 7,000 ppm. Specifically, it may be 50 to 7,000 ppm, 100 to 5,000 ppm, 100 to 2,000 ppm, or 200 to 1,000 ppm.

When the polymerization inhibitor is used to prepare the polyarylene sulfide resin, the emission of the polymerization inhibitor is reduced, thereby improving the removal efficiency of iodine. Therefore, the iodine content in the final polyarylene sulfide resin can be reduced.

In addition, the polyarylene sulfide resin may have a number average molecular weight of 2,000 to 50,000 g/mol when measured by high temperature gel permeation chromatography in a solvent of 1-chloronaphthalene. In particular, it may be 3,000 to 40,000 g/mol, 4,000 to 30,000 g/mol, or 5,000 to 20,000 g/mol.

The polyarylene sulfide resin may have a weight average molecular weight of 5,000 to 200,000 g/mol when measured by high temperature gel permeation chromatography in a solvent of 1-chloronaphthalene. In particular, it may be 10,000 to 150,000 g/mol or 20,000 to 100,000 g/mol.

The polyarylene sulfide resin may have a peak molecular weight of 3,500 to 125,000 g/mol when measured by high temperature gel permeation chromatography in a solvent of 1-chloronaphthalene. In particular, it may be 8,000 to 95,000 g/mol or 12,500 to 60,000 g/mol.

The polyarylene sulfide resin can have a melt viscosity of 100 to 50,000 poise when measured with a rotating disk viscometer at an angular frequency of 1.84 rad/s at 300°C. In particular, it may be 500 to 10,000 poise or 1,000 to 5,000 poise.

The polyarylene sulfide resin may have a nonlinear index of 0.001 to 0.5 when calculated by the following equation 1 measured with a rotating disk viscometer at 300°C. In particular, it may be 0.001 to 0.4, 0.001 to 0.3, or 0.003 to 0.2. [Equation 1] Nonlinear exponent = 1 - (melt viscosity at shear rate of ^{17.3 s -1} ) / (melt viscosity at shear rate of ^{3.22 s -1 )}

When a polymerization inhibitor is used to prepare a polyarylene sulfide resin, the emission of the polymerization inhibitor is suppressed in the decompression step during the production of the polyarylene sulfide resin, or the disulfide bond in the polyarylene sulfide resin is reduced during the reaction Rate. Therefore, the formation of a side chain structure in the polyarylene sulfide resin can be suppressed, and the linearity of the final polyarylene sulfide resin can be enhanced.

Since the polyarylene sulfide resin prepared with the polymerization inhibitor has a lower disulfide bond fraction or iodine content than the polyarylene sulfide resin prepared without the polymerization inhibitor, the disulfide bond fraction or the iodine content is lower, This results in excellent linearity. Therefore, it can have excellent physical properties such as strength and elongation. Therefore, polyarylene sulfide resins prepared using polymerization inhibitors can be particularly suitable for fibers and films. Example embodiments for carrying out the present invention

Hereinafter, the present invention will be described in detail with reference to examples. The following examples are merely illustrative of the present invention, and the scope of the present invention is not limited thereto. Example 1 : Synthesis of polyarylene sulfide resin 1 (PAS 1 )

A 5 liter reactor equipped with a thermocouple capable of measuring the internal temperature of the reactor and a vacuum line capable of nitrogen purging and vacuum application was charged with 5,240 g of p-diiodobenzene and 450 g of elemental sulfur. The composition containing p-diiodobenzene and elemental sulfur in the reactor was heated to 180°C to fully melt and mix. Thereafter, the polymerization reaction was performed while gradually increasing and decreasing the temperature and pressure from the initial reaction conditions of 220° C. and 200 Torr to the final reaction conditions of 300 to 320° C. and 0.5 Torr.

Samples of the polymerized reactants were collected at regular intervals, and the iodine content in the samples was measured by ion chromatography. When the residual iodine content reached a level of about 5% by weight based on the total weight of the polymerization, 50 g of 1,2-bis(2-benzamidephenyl-1-yl)disulfane (compound ( 29); TCI product number D1102; purity greater than 98%).

The reaction was further carried out at the same temperature and pressure. When the residual iodine content reached about 0.5 to 1 wt % based on the total weight of the polymerization reactants, the reaction was carried out for 10 minutes at 300° C. and 0.7 Torr in a nitrogen atmosphere. After that, the pressure was reduced to 0.5 Torr or less, and the reaction was further carried out for 1 hour. Subsequently, the reaction was terminated, and the resin thus prepared was processed into pellets using a small strand cutter to obtain about 1,540 g of a polyarylene sulfide resin. Example 2 : Synthesis of Polyarylene Sulfide Resin 2 (PAS 2 )

About 1,550 g of polyarylene sulfide resin was obtained in the same manner as in Example 1, except that when the residual iodine content reached about 10% by weight based on the total weight of the polymerized reactants, 50 g of 1,2- Bis(2-benzamidephenyl-1-yl)disulfane was added to the reactor. Example 3 : Synthesis of polyarylene sulfide resin 3 (PAS 3 )

About 1,490 g of polyarylene sulfide resin were obtained in the same manner as in Example 1, except that 50 g of 1,2-bis(2-benzamidephenyl-1-yl)disulfide were added in the initial stage Alkane is added to the reactor along with diiodobenzene and elemental sulfur. Example 4 : Synthesis of polyarylene sulfide resin 4 (PAS 4 )

About 1,600 g of polyarylene sulfide resin was obtained in the same manner as in Example 1, except that 52 g of 1,2-bis(3-(triethoxysilyl)propyl)disulfane (compound (22); SiSiB-PC2200 of Power Chemical (China Company) in place of 50 g of 1,2-bis(2-benzamidephenyl-1-yl)disulfane. Example 5 : Synthesis of polyarylene sulfide resin 5 (PAS 5 )

About 1,600 g of polyarylene sulfide resin was obtained in the same manner as in Example 2, except that 52 g of 1,2-bis(3-(triethoxysilyl)propyl)disulfane (compound (22)) in place of 50 g of 1,2-bis(2-benzamidephenyl-1-yl)disulfane. Example 6 : Synthesis of polyarylene sulfide resin 6 (PAS 6 )

About 1,580 g of polyarylene sulfide resin were obtained in the same manner as in Example 1, except that 35 g of 1-(naphthalen-2-yl)-2-(naphthalen-2-yl)disulfane (compound (1); Sigma-Aldrich Prod. No. S838594) instead of 50 g of 1,2-bis(2-benzamidephenyl-1-yl)disulfane. Example 7 : Synthesis of polyarylene sulfide resin 7 (PAS 7 )

About 1,540 g of polyarylene sulfide resin were obtained in the same manner as in Example 1, except that 52 g of 3-(triethoxysilyl)propane-1-thiol (compound (17); Power Chemical (Chinese company) SiSiB-PC2310) instead of 50 g of 1,2-bis(2-benzylaminophenyl-1-yl)disulfane. Example 8 : Synthesis of polyarylene sulfide resin 8 (PAS 8 )

About 1,510 g of polyarylene sulfide resin were obtained in the same manner as in Example 1, except that 52 g of 4-iodothiophenol (compound (26); according to Hiremath, R. et al., Chem . Mater . 2004 , 16 , 4948-4954 described in the synthesis) instead of 50 g of 1,2-bis(2-benzamidephenyl-1-yl)disulfane. Comparative Example 1 : Synthesis of Polyarylene Sulfide Resin 9 (PAS 9 )

About 1,420 g of polyarylene sulfide resin were obtained in the same manner as in Example 1, except that 24 g of diphenyl disulfide (Sigma-Aldrich product number 169021) was used instead of 50 g of 1,2-bis(2- benzamidophenyl-1-yl)disulfane. Comparative Example 2 : Synthesis of Polyarylene Sulfide Resin 10 (PAS 10 )

About 1,430 g of polyarylene sulfide resin was obtained in the same manner as in Example 2, except that 24 g of diphenyl disulfide was used instead of 50 g of 1,2-bis(2-benzylaminophenyl-1) - base) disulfane. Comparative Example 3 : Synthesis of Polyarylene Sulfide Resin 11 (PAS 11 )

About 1,430 g of polyarylene sulfide resin were obtained in the same manner as in Example 3, except that 24 g of diphenyl disulfide was used instead of 50 g of 1,2-bis(2-benzylaminophenyl-1) - base) disulfane. [ Test example ]

The polyarylene sulfide resins 1 to 11 prepared according to Examples 1 to 8 and Comparative Examples 1 to 3 were measured for melting point, melt viscosity, nonlinear index, molecular weight, branch ratio, disulfide bond fraction, and iodine content by the following methods Take measurements. The results are shown in Table 2 below. ( 1 ) Melting point (Tm )

In a differential scanning calorimeter (DSC, model Q20 from TA Instrument), the temperature was increased from 30°C to 320°C at a rate of 10°C/min, and then the temperature was cooled to 30°C, followed by 10°C/min The temperature was raised again from 30°C to 320°C at a rate of minutes to measure the melting point. ( 2 ) melt viscosity ( MV ) and nonlinear index

The melt viscosity is defined as the viscosity at an angular frequency of 1.84 rad/s when the viscosity is measured by the frequency sweep method at 300°C with a rotating disk viscometer in the angular frequency range of 0.6 to 500 rad/s.

The nonlinear index is calculated by Equation 1 below. [Equation 1] Nonlinear index = 1 - (melt viscosity at shear rate of ^{17.3 s -1} ) / (melt viscosity at shear rate of ^{3.22 s -1} ) (3 ) number average molecular weight (Mn ) , weight Average Molecular Weight (Mw ) and Peak Molecular Weight (Mp )

The number average molecular weight, weight average molecular weight and peak molecular weight of the polyarylene sulfide resin were measured by gel permeation chromatography under the following measurement conditions. In all measurements of molecular weight, six types of monodisperse polystyrene were used for calibration. [Measurement conditions for gel permeation chromatography] Instrument: Agilent PL-220 Column: Agilent, PLgel pore size 105Å + 104Å + 500Å + 50Å (4 types of columns) Column temperature: 210°C Solvent: 1-chloronaphthalene Measurement method: triple system detector (RI, viscometer, light scatterer 15° and 90°) (4 ) Branch ratio ( α )

The branching ratio is defined as the value of alpha calculated by applying the viscosity measured according to the triple system detector to the Mark-Houwink equation of Equation 2 below. The Mark-Houwink equation is the relationship between the molecular weight of the polymer and the intrinsic viscosity, and the branching ratio (α) represents the degree of branching of the polymer. That is, the closer the value is to 1, the more linear the polymer is. The closer the value is to 0, the higher the degree of polymer branching. [Equation 2] [η] = KХMα

In the above equation, η is the intrinsic viscosity, M is the weight average molecular weight, and K is a constant. (5) disulfide bonds (-S -S -) fraction

The disulfide bond fraction is calculated by Equation 3 below. [Equation 3] Disulfide bond fraction (wt%) = {(total weight of sulfur detected by elemental analysis) - (theoretical weight of sulfur in polyarylene sulfide)} / (sulfur in polyarylene sulfide The theoretical weight) (6 ) iodine content

The iodine content in the polyarylene sulfide resin was measured by ion chromatography (IC) using Thermo Scientific IC (AQF) and ICS-2500 (Mitsubishi AQF-100). [Table 2] Tm (°C) MV (poise) -SS- fraction (wt%) Iodine content (ppm) Mn (g/mol) Mw (g/mol) Mp (g/mol) alpha nonlinear index Example 1 280.2 2,010 0.18 800 10,068 42,156 26,588 0.67 0.09 Example 2 279.5 1,980 0.13 560 8,866 41,752 27,163 0.63 0.11 Example 3 279.3 2,200 0.05 249 8,373 43,834 26,305 0.61 0.13 Example 4 281.4 1,910 0.19 990 10,116 38,165 28,051 0.68 0.07 Example 5 280.9 1,898 0.12 610 9,611 40,637 28,354 0.66 0.08 Example 6 282.0 2,090 0.16 700 8,608 39,965 26,874 0.67 0.09 Example 7 282.5 1,965 0.12 1,300 9,890 44,899 29,798 0.63 0.11 Example 8 282.3 1,890 0.02 2,500 11,090 46,020 29,087 0.60 0.09 Comparative Example 1 281.5 2,190 0.29 2,300 10,800 43,029 27,200 0.58 0.12 Comparative Example 2 281.2 2,200 0.28 1,800 9,800 42,390 26,884 0.55 0.14 Comparative Example 3 280.8 1,990 0.27 1,400 8,990 39,020 27,790 0.51 0.17

Among the polyarylene sulfide resins of Examples 1, 4, and 6 to 8 and Comparative Example 1 prepared under the same conditions except for the kind of polymerization inhibitor, Example 1 prepared using a compound represented by one of Formulae 1 to 4 The polyarylene sulfide resins of , 4, and 6 to 8 have excellent linearity because they have a lower nonlinear index and a significantly higher branching ratio than the polyarylene sulfide resin of Comparative Example 1.

In particular, the polyarylene sulfide resins of Examples 1, 4, 6 and 7 prepared using compounds represented by one of formulae 1 to 3 had significantly lower iodine content than the polyarylene sulfide resin of Comparative Example 1 . Meanwhile, the polyarylene sulfide resin of Example 8 prepared using the compound represented by Formula 4 had a significantly lower disulfide bond ratio than the polyarylene sulfide resin of Comparative Example 1.

In the polyarylene sulfide resins of Examples 2 and 5 and Comparative Example 2 prepared under the same conditions except for the kind of polymerization inhibitor, or in Example 2 and Comparative Example 3 prepared under the same conditions except for the kind of polymerization inhibitor In the polyarylene sulfide resin, it exhibits the same trend.

Meanwhile, in the polyarylene sulfide resins of Examples 1 to 3 prepared under the same conditions except for the timing of adding the polymerization inhibitor, the later the polymerization inhibitor was added, the lower the nonlinear index and the higher the molecular weight and branching ratio. , resulting in better linearity; and the earlier the polymerization inhibitor is added, the lower the disulfide bond fraction and the iodine content.

The same trend is confirmed in the results of Examples 4 and 5 and the results of Comparative Examples 1-3.

Claims (14)

A polymerization inhibitor for a polyarylene sulfide resin, comprising a compound represented by one of formulae 1 to 4: [Formula 1]

wherein X ¹ and X ² are each independently selected from the group consisting of: a hydrogen group, a halogen group, an alkyl group having 1 to 3 carbon atoms, -OA ¹ , -SA ² , -COOA ^{3 , -NA 4} A ⁵ , -SO ₃ A ⁶ and -NHCOA ⁷ , Z ¹ to Z ⁴ are each independently selected from the group consisting of a hydrogen group, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms and a substituted or unsubstituted alkenyl group having 1 or 2 carbon atoms, and p ¹ and p ² are each independently 1 or 2, wherein when Z ¹ and Z ² are an alkenyl group having 2 carbon atoms and when bonded to two adjacent carbon atoms, they can be connected to each other to form a benzene ring, when Z ³ and Z ⁴ are an alkenyl group having 2 carbon atoms and are bonded to two adjacent carbon atoms , which can be attached to each other to form a benzene ring, and A ¹ to A ⁷ are each independently selected from the group consisting of: a hydrogen group, a sodium cation, a lithium cation, a meridian having 1 to 3 carbon atoms Substituted or unsubstituted alkyl, one substituted or unsubstituted phenyl and one substituted or unsubstituted naphthyl, wherein A ¹ to A ⁷ the substituted alkyl group having 1 to 3 carbon atoms, the substituted or unsubstituted The phenyl group and the substituted naphthyl group each independently have a substituent selected from the group consisting of a thiol group and a phenyl sulfide group, and the substituents of Z ¹ to Z ⁴ having 1 or 2 carbon atoms The substituted alkyl and the substituted alkenyl having 1 or 2 carbon atoms each independently have a substituent selected from the group consisting of: a halogen, a hydroxyl, a thiol, a carboxyl, a amine and a sulfonic acid group, with the limitation that when X ¹ and X ² are both hydrogen atoms, ^{at least one of Z 1} and Z ² and Z ³ and Z ⁴ forms a substituted or unsubstituted benzene ring; [Formula 2]

wherein R ¹ to R ⁴ are each independently selected from the group consisting of a hydrogen group, a halogen group, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, -OA ⁸ , -SA ⁹ , ^{-COOA 10} , -NA ¹¹ A ¹² , -SO ₃ A ¹³ and -NHCOA ¹⁴ , wherein A ⁸ to A ¹⁴ are each independently selected from the group consisting of: a hydrogen group, a sodium cation, a lithium cation, and a group having A substituted or unsubstituted alkyl group of 1 to 3 carbon atoms, and the substituted alkyl group of R ¹ to R ⁴ with 1 to 5 carbon atoms and the substituted alkyl group of A ⁸ to A ¹⁴ with 1 to 3 carbon atoms The substituted alkyl groups of 1 carbon atoms each independently have a thiol group as a substituent, provided ^{that at least one of R 1} to R ⁴ is a substituted alkyl group having 1 to 5 carbon atoms, or ^{at least one of R 1} to R ⁴ is selected from the group consisting of -OA ⁸ , -SA ⁹ , -COOA ^{10 , -NA 11} A ¹² , -SO ₃ A ¹³ and -NHCOA ¹⁴ , and A ⁸ to A ¹⁴ is a substituted alkyl group having 1 to 3 carbon atoms; [Formula 3]

wherein X ⁷ to X ¹² are each independently selected from the group consisting of: a hydrogen group, a halogen group, an alkyl group having 1 to 5 carbon atoms, -OA ¹⁵ , -SA ¹⁶ , -COOA ^{17 , -NA 18} A ¹⁹ , -SO ₃ A ²⁰ and -NHCOA ²¹ , and R ⁵ and R ⁶ are each independently an alkylene group having 1 to 5 carbon atoms, wherein A ¹⁵ to A ²¹ are each independently selected from the following composition The group: a hydrogen group, a sodium cation, a lithium cation and a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and the one having 1 to 5 carbon atoms in A ¹⁵ to A ²¹ The substituted alkyl groups each independently have a thiol group as a substituent; and [Formula 4]

wherein X ^{13 is} each independently selected from the group consisting of: a hydrogen group, a halogen group, an alkyl group having 1 to 5 carbon atoms, OA ²² , -SA ²³ , -COOA ^{24 , -NA 25} A ²⁶ , -SO ₃ A ²⁷ and -NHCOA ²⁸ , Z ⁵ and Z ⁶ are each independently selected from the group consisting of a hydrogen group, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a group having 1 or substituted or unsubstituted alkenyl of 2 carbon atoms, w is a halogen group, and q is each independently an integer from 1 to 3, wherein when Z ⁵ and Z ⁶ are an alkene having 2 carbon atoms When bonded to two adjacent carbon atoms, which can be linked to each other to form a benzene ring, A ²² , A ²⁴ and A ²⁵ are each independently selected from the group consisting of: a sodium cation, a lithium cation, A substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group, and A ²³ and A ²⁶ to A ²⁸ are each independently selected from The group consisting of: a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted phenyl group Naphthyl, wherein A ²² to A ²⁸ of the substituted alkyl group having 1 to 5 carbon atoms, the substituted phenyl group and the substituted naphthyl group each independently have a thiol group and a phenylthio group selected from A substituent of the group consisting of ether groups, and ^{the substituted alkyl group with 1 or 2 carbon atoms of Z 5} to Z ⁶ and the substituted alkenyl group with 1 or 2 carbon atoms each independently have a group selected from A monosubstituent of the group consisting of a halogen group, a hydroxyl group, a thiol group, a carboxyl group, an amine group and a sulfonic acid group. The polymerization inhibitor for a polyarylene sulfide resin according to claim 1, wherein the compound represented by one of formulae 1 to 4 is at least one selected from the following compounds (1) to (31): (1) 1-(Naphthalene-2-yl)-2-(naphthalene-2-yl)disulfane (2) 1-(Naphthalene-1-yl)-2-(naphthalene-1-yl)disulfane (3) 1-(Naphthalene-1-yl)-2-(naphthalene-2-yl)disulfane (4) 1-(Naphthalene-1-yl)-2-benzenedisulfane (5) 1,2-bis(2-iodonaphthalen-6-yl)disulfane (6) 1,2-bis(1-iodonaphthalen-5-yl)disulfane (7) 1-(1-iodonaphthalen-5-yl)-2-(2-iodonaphthalene-6-yl)disulfane (8) 1-(1-iodonaphthalen-5-yl)-2-(4-iodophenyl)disulfane (9) 1,2-bis(2-carboxynaphthalen-6-yl)disulfane (10) 1,2-bis(2-hydroxynaphthalen-6-yl)disulfane (11) 1,2-bis(2-aminonaphthalen-6-yl)disulfane (12) 1,2-bis(2-mercaptonaphthalen-6-yl)disulfane (13) 1,2-bis(1-carboxynaphthalen-4-yl)disulfane (14) 4-(2-(1-Hydroxynaphthalen-4-yl)disulfanyl)naphthalene-1-carboxylic acid (15) 4-(2-(1-Hydroxynaphthalen-2-yl)disulfanyl)naphthalene-1-ol (16) 5-(2-(2-Hydroxynaphthalen-6-yl)disulfanyl)naphthalene-1-ol (17) 3-(Triethoxysilyl)propane-1-thiol (18) 3-(Trimethoxysilyl)propane-1-thiol (19) 3-(Hydroxydimethoxysilyl)propane-1-thiol (20) 3-(Trihydroxysilyl)propane-1-thiol (21) 3-(Dihydroxysilyl)propane-1-thiol (22) 1,2-bis(3-(triethoxysilyl)propyl)disulfane (23) 1,2-Bis(3-(trihydroxysilyl)propyl)disulfane (24) 1,2-Bis(3-(trimethoxysilyl)propyl)disulfane (25) 1-(3-(Triethoxysilyl)propyl)-2-(3-(trihydroxysilyl)propyl)disulfane (26) 4-Iodothiophenol (27) 1-ethoxy-4-iodobenzene (28) Ethyl(4-iodophenyl)sulfane (29) 1,2-Bis(2-benzylaminophenyl-1-yl)disulfane (30) 1,2-Bis(2-naphtholin-1-yl)disulfane (31) 1,2-bis(2-(4-(phenylthio)benzylamino)phenyl-1-yl)disulfane A polyarylene sulfide resin composition comprising a diiodo aromatic compound, a monosulfur compound and the polymerization inhibitor for a polyarylene sulfide resin as claimed in claim 1. The polyarylene sulfide resin composition of claim 3, wherein the polymerization inhibitor is contained in an amount of 0.00001 to 5% by weight based on the total weight of the composition. A method for preparing a polyarylene sulfide resin, comprising melting a composition comprising a diiodo aromatic compound, a monosulfur compound and a polymerization inhibitor for a polyarylene sulfide resin as claimed in claim 1 polymerization. The method for preparing a polyarylene sulfide resin according to claim 5, wherein the melt polymerization step is carried out under high temperature and reduced pressure conditions at a temperature of 180 to 400° C. and a pressure of 0.001 to 500 Torr. A polyarylene sulfide resin prepared by melt-polymerizing a composition comprising a diiodo aromatic compound, a monosulfur compound, and the polymerization inhibitor for a polyarylene sulfide resin as claimed in claim 1. The polyarylene sulfide resin of claim 7, wherein the content of a disulfide bond in the polyarylene sulfide resin is 0.001 to 0.25% by weight. The polyarylene sulfide resin of claim 7, wherein the branching ratio of the polyarylene sulfide resin is 0.6 to 1.0. The polyarylene sulfide resin of claim 7, wherein the iodine content in the polyarylene sulfide resin is 50 to 7,000 ppm. The polyarylene sulfide resin of claim 7, when measured by high temperature gel permeation chromatography in 1-chloronaphthalene as a solvent, has a number average molecular weight of 5,000 to 20,000 g/mol. The polyarylene sulfide resin of claim 7, when measured by high temperature gel permeation chromatography in 1-chloronaphthalene as a solvent, has a weight average molecular weight of 20,000 to 100,000 g/mol. The polyarylene sulfide resin of claim 7 has a melt viscosity of 100 to 50,000 poise when measured with a rotating disk viscometer at an angular frequency of 1.84 rad/s at 300°C. The polyarylene sulfide resin of claim 7, having a non-linearity index of one of 0.001 to 0.4 when measured by the following equation 1 at 300°C with a rotating disk viscometer: [Equation 1] Non- Linearity Index = 1 - ( ^{melt viscosity at a shear rate of 17.3 s -1} ) / (melt viscosity at a shear rate of 3.22 s ^-1 ).