KR20210141891A - Resin composition for water-related component and water-related component comprising the same - Google Patents

Abstract

The present invention relates to a novel polyarylene sulfide resin composition for a water-related component and a water-related component comprising the same, wherein the resin composition for a water-related component of the present invention has a small amount of gas out, excellent cavity balance, excellent tensile strength, excellent tensile elongation, excellent impact strength and/or excellent creep resistance. According to one embodiment, provided is a resin composition for a water-related component comprising: a post-processed first polyarylene sulfide resin in which a terminal group derived from a compatibilizer is introduced into a first polyarylene sulfide resin obtained by melt polymerization of a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor; and an additive.

Description

Resin composition for water section parts and water section parts comprising the same

The embodiment relates to a resin composition for a water section component and a water section component comprising the same.

A metal material has been used for a pipe for transferring a high-temperature fluid used in a heat exchanger, a hot water supply device, a food waste treatment device, and the like, but a plastic material is recently used. As a plastic material for piping, polyarylene sulfide resin having excellent heat resistance and mechanical strength is used.

Polyphenylene sulfide is the only polyarylene sulfide currently being mass-marketed, and its production method includes a solution polymerization method in which paradichlorobenzene and sodium sulfide are polymerized as raw materials in N-methylpyrrolidone solvent (patented). Reference 1), there is a melt polymerization method in which a diiodine aromatic compound and a sulfur compound are polymerized at a high temperature as raw materials without using a solvent.

The polyphenylene sulfide resin prepared by the solution polymerization method is known to adversely affect the heat resistance, flame resistance and durability of the molded article because of the use of a solvent and the amount of outgas due to chlorine contained in the raw material.

The polyphenylene sulfide resin prepared by the melt polymerization method does not use a solvent, so it has excellent productivity and cost structure, has a low amount of outgas, and has improved effects such as excellent corrosion resistance because it does not use a chlorine-based raw material. However, due to the non-polar end group of the resin, it is difficult to modify it to have desired properties due to its low reactivity with processing additives, which limits its use or usage, and the disulfide bond derived from the sulfur compound used as a raw material has a weak structure in the resin. There is a limit in that the mechanical strength is not sufficient because it acts as a

On the other hand, polyarylene sulfide resin is widely used as a plastic material for piping due to its excellent heat resistance and mechanical strength. have.

Therefore, in order to improve the freezing resistance of a pipe made of polyarylene sulfide resin, a technology for preventing breakage, rupture, etc. due to freezing of the internal fluid by increasing the flexibility of the resin composition by mixing a thermoplastic elastomer with the polyarylene sulfide resin It is known (refer patent document 2).

US Patent No. 2,513,188 Japanese Patent Laid-Open No. 2004-300271

Molded articles manufactured using the polyarylene sulfide resin composition blended with a thermoplastic elastomer exhibit improved freezing resistance, but when used for piping, when used in piping, when in contact with high-temperature fluids such as hot water for a long time due to increased flexibility There is another problem in that the deformation of the pipe itself is increased and the creep resistance is lowered, which causes a gap at the interface with other metal parts in contact with the pipe, which may cause a high-temperature fluid inside the pipe to leak.

As a result of intensive research to solve this problem, the present inventors have found that, when polyarylene sulfide resin post-processed with a compatibilizer is used for the manufacture of water section parts, mechanical strength such as tensile strength and impact strength, etc., while improving creep resistance found that it can be done. In addition, the present invention was completed by discovering that a water section part having excellent mechanical strength and creep resistance can be manufactured by mixing a solution-polymerized polyarylene sulfide resin and a melt-polymerized polyarylene sulfide resin.

Accordingly, in the embodiments described below, it is an object to provide a novel polyarylene sulfide resin composition for water section parts and water section parts including the same.

According to one embodiment, the diiodo aromatic compound, the first sulfur compound and the polymerization inhibitor are melt-polymerized in the first polyarylene sulfide resin, a post-processed first polyarylene sulfide resin in which end groups derived from a compatibilizer are introduced; And, comprising an additive, a resin composition for water section parts is provided.

According to another embodiment, a diiodo aromatic compound, a first sulfur compound, and a first polyarylene sulfide resin in which the polymerization inhibitor is melt-polymerized; a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound; And, comprising an additive, a resin composition for water section parts is provided.

According to another embodiment, a post-processed first polyarylene sulfide in which a terminal group derived from a compatibilizer is introduced into a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized. profit; a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound; And, comprising an additive, a resin composition for water section parts is provided.

According to another embodiment, there is provided a water section part including a molded article molded with the above-described resin composition for the water section part.

According to another embodiment, a pipe for a fluid is provided, including a molded article in which the above-described resin composition for water section parts is molded.

The polyarylene sulfide resin composition for water section parts of the embodiment may have a low outgas amount, excellent cavity balance, tensile strength, tensile elongation, impact strength, and/or creep resistance.

Hereinafter, the invention will be described in detail through embodiments. The embodiments are not limited to the contents disclosed below and may be modified in various forms as long as the gist of the invention is not changed.

[Post-processed polyarylene sulfide resin composition]

According to the embodiment, the first polyarylene sulfide resin is post-processed in which terminal groups derived from a compatibilizer are introduced into the first polyarylene sulfide resin in which the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor are melt-polymerized; and an additive, a resin composition for water section parts (hereinafter, post-processed first polyarylene sulfide resin composition) is provided.

According to another embodiment, preparing a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; mixing an additive and the first polyarylene sulfide resin; and post-processing the first polyarylene sulfide resin using a compatibilizer.

First polyarylene sulfide resin

The first polyarylene sulfide resin may be prepared by melt polymerization of a composition including a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor.

The diiodo aromatic compound refers to a compound having an aromatic ring and two iodine atoms directly bonded thereto. Diiodo aromatic compounds include diiodobenzene, diiodotoluene, diiodoxylene, diiodonaphthalene, diiodobiphenyl, diiodobenzophenone, diiododiphenyl ether and diiododiphenyl. It may be at least one selected from the group consisting of sulfones, but is not limited thereto.

The aromatic ring of the diiodo aromatic compound is a halo group excluding an iodo group, a phenyl group, a hydroxy group, a nitro group, an amino group, an alkoxy group having 1 to 6 carbon atoms, a carboxy group, a carboxylate, an arylsulfone and an aryl ketone from the group consisting of It may be substituted by at least one selected substituent. When the aromatic ring of the diiodo aromatic compound is substituted by the substituent, the diiodo aromatic compound having an aromatic ring substituted with the substituent is a diiodo having an unsubstituted aromatic ring from the viewpoint of crystallinity and heat resistance of the resin. It may also be 0.0001 to 5% by weight or 0.001 to 1% by weight based on the aromatic compound. Substitution positions of two iodo groups present in the diiodo aromatic compound are not particularly limited, but the two substitution positions may be at positions far from each other in the molecule, and may be para positions or 4,4'-positions.

The diiodo aromatic compound is present in an amount of 0.5 to 2.0 moles, 0.55 to 1.9 moles, 0.6 to 1.8 moles, 0.65 to 1.7 moles, 0.7 to 1.6 moles, 0.75 to 1.5 moles, or 0.8 to 1.4 moles based on 1 mole of the first sulfur compound. can be included as The diiodo aromatic compound may be, for example, p-diiodobenzene.

The first sulfur compound may be a single sulfur. Single sulfur refers to a compound composed of sulfur atoms. The single sulfur may be at least one selected from the group consisting of _{S 8} , S ₆ , S ₄ and S _{2 , and specifically, it may be a mixture containing S 8} and S ₆ that is generally available, but limited thereto doesn't happen The purity, form, and particle size of the single sulfur are not particularly limited. For example, the form of single sulfur may be in the form of granules or powders which are solid at room temperature (23° C.). In addition, the particle diameter of the single sulfur may be 0.001 to 10 mm, 0.01 to 5 mm, or 0.01 to 3 mm, but is not particularly limited thereto.

The polymerization inhibitor may be used without particular limitation as long as it is a compound that inhibits or stops the polymerization reaction of the first polyarylene sulfide resin. The polymerization inhibitor is a compound capable of introducing at least one functional group selected from the group consisting of -OR, -SR, -COOR, -NHR, -SO _{3 R, -NHCOR, etc. at the end of the main chain of the polyarylene sulfide resin} may be, wherein R may each independently be a hydrogen group, a metal cation such as sodium or lithium, a halo group, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. The polymerization inhibitor may include the functional group, and the functional group may be generated by a polymerization stop reaction or the like. In addition, the polymerization inhibitor may be a compound not containing the functional group, specifically, diphenyl disulfide, monoiodobenzene, thiophenol, 2,2'-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole , N-cyclohexyl-2-benzothiazolylsulfenamide, 2-(morpholinothio)benzothiazole and N,N'-dicyclohexyl-1,3-benzothiazole-2-sulfenamide at least one compound.

In addition, the polymerization inhibitor may be one or more of the compounds represented by the following Chemical Formulas 1 to 3, specifically, may be a compound represented by the Chemical Formula 1.

[Formula 1]

X ¹ and X ² are each independently a hydrogen group, a halo group, an alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted phenyl group, -OA ¹ , -SA ² , -COOA ³ , ^{-NA 4} A ⁵ , - SO ₃ A ⁶ and -NHCOA ⁷ is selected from the group consisting of, A ¹ to A ⁷ are each independently a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and a substituted or unsubstituted is selected from the group consisting of a substituted phenyl group, Z ¹ to Z ⁴ are each independently a hydrogen group, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted alkenyl having 1 or 2 carbon atoms It is selected from the group consisting of a group, and m ¹ and m ² are each independently an integer of 1 to 3.

When Z ¹ and Z ² are an alkenyl group having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring. In addition, when Z ³ and Z ⁴ are alkenyl groups having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring.

When m ¹ or m ² is 2 or more, two or more X ¹ or X ² bonded to one aromatic ring may be the same as or different from each other. In addition, Z ¹ and Z ³ may be the same as or different from each other, and Z ² and Z ⁴ may be the same or different from each other.

The substituted phenyl group of X ¹ or X ² may have a substituent of -SH or -SS-Ph. In addition, ^{the substituted alkyl group having 1 to 3 carbon atoms and the substituted phenyl group of A 1} to A ⁷ may have a substituent of an alkyl group or phenyl group having 1 or 2 carbon atoms.

Z ¹ and Z ² may be bonded to two adjacent carbon atoms, and Z ³ and Z ⁴ may be bonded to two adjacent carbon atoms.

In addition, at least one or two or more of ^{Z 1} to Z ^{4 may not be a hydrogen group.} In addition, at least one of ^{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 .} Also, for example, ^{when both X 1} and X ² are hydrogen groups, ^{at least one of a combination of Z 1} and Z ² or a combination of Z ³ and Z ⁴ may be connected to each other to form a benzene ring.

[Formula 2]

X ^{3 To} X ⁶ are each independently a hydrogen group, a halo group, an alkyl group having 1 to 5 carbon atoms, -OA ⁸ , -SA ⁹ , -COOA ¹⁰ , ^{-NA 11} A ¹² , -SO ₃ A ¹³ and -NHCOA is selected from the group consisting of ^{14 , and A 8} to A ¹⁴ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 3 carbon atoms, and R ¹ to R ⁴ are each independently It is selected from the group consisting of an alkylene group having 1 to 5 carbon atoms and an alkoxy group.

At least one of X ³ to X ⁶ 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 .} In addition, at least one of ^{X 3} to X ⁶ may be ^{-SA 9 in which A 9} is a hydrogen group.

[Formula 3]

X ⁷ to X ¹² are each independently a hydrogen group, a halo 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 is selected from the group consisting of ^{21 , A 15} to A ²¹ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, and an alkyl group having 1 to 5 carbon atoms, R ⁵ and R ⁶ are each independently It is an alkylene group having 1 to 5 carbon atoms.

In addition, the polymerization inhibitor may be included in an amount of 0.0001 to 0.1 moles, 0.0002 to 0.08 moles, 0.0005 to 0.05 moles, or 0.001 to 0.05 moles based on 1 mole of the first sulfur compound.

Meanwhile, in the melt polymerization, a catalyst may be additionally used. The catalyst may be, for example, a nitrobenzene-based catalyst, and specifically may be at least one selected from the group consisting of 1,3-diiod-4-nitrobenzene and 1-iod-4-nitrobenzene, but is not limited thereto. When the catalyst is used, it may be used in an amount of 0.0001 to 0.1 moles, 0.0002 to 0.05 moles, or 0.0005 to 0.01 moles based on 1 mole of the first sulfur compound.

Melt polymerization may proceed under any conditions as long as the polymerization reaction of the composition including the diiodo aromatic compound and the first sulfur compound can be initiated. For example, melt polymerization may be carried out at a temperature of about 180 to 400 °C, 180 to 350 °C, or 180 to 300 °C, and at a pressure of about 0.001 to 500 torr, 0.001 to 450 torr, or 0.001 to 400 torr. . More specifically, melt polymerization may proceed under elevated temperature and reduced pressure reaction conditions. In this case, temperature rise and pressure drop are performed under initial reaction conditions of a temperature of about 180 to 250° C. and a pressure of about 50 to 450 torr, which is the final reaction condition. Changed to about 270 to 350 ℃ and pressure of about 0.001 to 20 torr, it can proceed for about 0.1 to 30 hours. More specifically, melt polymerization may be performed under the final reaction conditions at a temperature of about 280 to 300° C. and a pressure of about 0.1 to 2 torr.

Meanwhile, the order of mixing the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor is not particularly limited, but the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor are simultaneously mixed, or the diiodo aromatic compound and a polymerization inhibitor may be mixed with a mixture including the first sulfur compound to prepare a composition for melt polymerization.

When the polymerization inhibitor is not mixed with the diiodo aromatic compound and the first sulfur compound at the same time, the timing of adding the polymerization inhibitor is not particularly limited, but may be determined in consideration of the final molecular weight of the target polyarylene sulfide. For example, about 0 to 30% by weight, 30 to 70% by weight, or 70 to 100% by weight of the diiodine aromatic compound contained in the initial reactant may be added at a time when the reaction is exhausted. Alternatively, the timing of the polymerization inhibitor may be added when the molecular weight of the polymerization product reaches a certain level. For example, the molecular weight of the polymerization reactant is 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% of the final molecular weight of the target polyarylene sulfide. % or more, 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, a polymerization inhibitor may be added. The molecular weight of the polymerization reactant can be determined, for example, through gel permeation chromatography.

In addition, before the polymerization inhibitor is added, the composition including the diiodine aromatic compound and the first sulfur compound may be melt-mixed. In this case, a catalyst may also be included in the composition in the melt mixing step. The melt mixing is not particularly limited as long as all of the compositions can be melt-mixed. For example, the melt mixing may be performed at a temperature of about 130 to 200°C or about 160 to 190°C. In the case of performing such melt mixing, melt polymerization to be performed later may be more easily performed.

First polyarylene sulfide resin post-processed with compatibilizer

The post-processed first polyarylene sulfide resin may be prepared by post-processing the first polyarylene sulfide resin using a compatibilizer.

In addition, the post-processed first polyarylene sulfide resin may include a first polyarylene sulfide resin; and end groups derived from compatibilizers.

The first polyarylene sulfide resin is as described above.

The compatibilizer for post-processing the first polyarylene sulfide resin may be a compound including a functional group such as a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group. Specifically, the compatibilizer may be one or more of the compounds represented by one of the following Chemical Formulas 4 to 6.

[Formula 4]

Y ₁ and Y ₂ are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ¹ , -SB ² , -COOB ³ , -NB ⁴ B ⁵ , -SO ₃ B ⁶ and -NHCOB ⁷ , B ¹ to B ⁷ 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 3 carbon atoms, and a substituted or unsubstituted phenyl group, Z ^1' to Z ^{4 '} are each independently selected from the group consisting of a hydrogen group, an alkyl group having 1 or 2 carbon atoms, and an alkenyl group having 1 or 2 carbon atoms, and p ¹ and p ² are each independently an integer of 1 to 3, provided that At least one of , Y ₁ and Y ₂ is selected from the group consisting _{of -OB 1} , -SB ₂ , -COOB ₃ , -NB ₄ B ₅ , -SO ₃ B ₆ and -NHCOB _{7 .}

When Z ¹ ' and Z ² ' are alkenyl groups having 2 carbon atoms and bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring, and Z ³ ' and Z ⁴ ' are 2 carbon atoms When it is an alkylene group and is bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring.

When p ¹ or p ² is two or more, two or more Y ¹ or Y ² bonded to one aromatic ring may be the same as or different from each other. Further, Z ¹ ′ and Z ³ ′ may be the same as or different from each other, and Z ² ′ and Z ⁴ ′ may be the same or different from each other.

The substituted alkyl group of 1 or 2 carbon atoms or the substituted alkenyl group of 1 or 2 carbon atoms of ^{Z 1'} to Z ^{4' may have a substituent of an alkyl group or phenyl group of 1 or 2 carbon atoms.}

One of B ¹ to B ⁷ may have a substituted alkyl group having 1 to 3 carbon atoms or a substituted phenyl group having a substituent of an alkyl group or phenyl group having 1 or 2 carbon atoms.

Z ¹ ′ and Z ² ′ may be bonded to two adjacent carbon atoms, and Z ³ ′ and Z ⁴ ′ may be bonded to two adjacent carbon atoms. In addition, at least one or two or more of ^{Z 1} ′ to Z ^{4 ′ may not be a hydrogen group.}

[Formula 5]

Y ^{3 To} Y ⁶ are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ⁸ , -SB ⁹ , -COOB ¹⁰ , -NB ¹¹ B ¹² , -SO ₃ B ¹³ and -NHCOB ¹⁴ B ⁸ to B ¹⁴ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation and an alkyl group having 1 to 3 carbon atoms, and R ¹ ' to R ⁴ ' are each independently selected from the group consisting of 1 to 5 carbon atoms. It is selected from the group consisting of an alkylene group and an alkoxy group, with the proviso that at least one of ^{Y 3} to Y ^{6 is -OB 8} , -SB ⁹ , -COOB ¹⁰ , -NB ¹¹ B ¹² , -SO ₃ B ¹³ and -NHCOB ¹⁴ selected from the group consisting of Here, at least one of ^{Y 3} to Y ⁶ may be ^{—SB 9 in which B 9} is a hydrogen group.

[Formula 6]

Y ⁷ to Y ¹² are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ¹⁵ , -SB ¹⁶ , -COOB ¹⁷ , -NB ¹⁸ B ¹⁹ , -SO ₃ B ²⁰ and -NHCOB ²¹ , B ¹⁵ to B ²¹ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation and an alkyl group having 1 to 5 carbon atoms, and R ⁵ ′ and R ⁶ ′ are each independently selected from the group consisting of 1 to 5 carbon atoms. It is an alkylene group.

In addition, specifically, the compatibilizer is selected from the group consisting of 2,2'-dithiobisdibenzoic acid, 4,4'-aminophenyl disulfide, bis(3-hydroxyphenyl) disulfide and bis(4-hydroxyphenyl) disulfide. It may be at least one selected, but is not particularly limited thereto.

The compatibilizer may perform a substitution reaction with an iodine atom that may be positioned at the terminal of the first polyarylene sulfide resin, or may serve as a compatibilizer by itself without a reaction. When the first polyarylene sulfide resin is post-processed with a compatibilizer, the atmosphere of the main chain and/or the terminal of the first polyarylene sulfide resin can be changed from hydrophobic to hydrophilic, and through this, other resins having hydrophilic functional groups and/or reactive groups , it is possible to improve the compatibility with inorganic fillers, etc., it is possible to improve the mechanical strength of the final product using the same and to significantly reduce the amount of outgas generated by heating.

The compatibilizer may react with the first polyarylene sulfide resin to impart end groups to the first polyarylene sulfide resin. Accordingly, the post-processed first polyarylene sulfide resin may have end groups derived from the compatibilizer.

The terminal group derived from the compatibilizer may mean a functional group of the compatibilizer. Specifically, the compatibilizer may be a compound containing a functional group such as a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, or a sulfonate group, so the terminal group derived from the compatibilizing agent is also carboxyl It may be a functional group, such as a group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group.

More specifically, the terminal group derived from the compatibilizer may have a structure represented by one of the following Chemical Formulas 7 to 9.

[Formula 7]

[Formula 8]

[Formula 9]

In the above formula, Z ¹ ', Z ² ', Y ¹ , Y ³ to Y ⁵ , Y ⁷ to Y ⁹ , R ¹ ' to R ⁵ ' and p ¹ are the same as described above.

The compatibilizer may be included in an amount of 0.001 to 10% by weight, 0.001 to 5% by weight, 0.01 to 3% by weight, or 0.1 to 2% by weight based on the total weight of the first polyarylene sulfide resin. When the first polyarylene sulfide resin is post-processed using a compatibilizing agent after polymerization, the reaction efficiency of the compatibilizing agent is significantly better than when the same compound is added as a polymerization inhibitor during the polymerization of the resin. The content of the functional group can be maximized, and the target content of the functional group to be introduced into the final resin can be achieved through the compatibilizer while using a small amount of the compatibilizer. When the same compound is added as a polymerization inhibitor, the reaction efficiency is low because the compound is decomposed by a high-temperature environment required for the polymerization reaction or discharged during the reaction. Furthermore, when added during polymerization of the first polyarylene sulfide resin, it is possible to minimize byproducts that may be generated by the compatibilizer. Therefore, when the first polyarylene sulfide resin is post-processed with a compatibilizer, the amount of outgas is reduced by reducing the amount of polymerization inhibitor / compatibilizer that can be a cause of outgas, and by-products are minimized, and at the same time, compatibility is improved. Physical properties such as tensile strength, impact strength, and creep resistance can be improved. In addition, the first polyarylene sulfide resin post-processed with a compatibilizer has an effect of reducing the production cycle as well as excellent cavity balance by improving processability in the injection process as the amount of outgas is reduced as described above. can

Post-processing using a compatibilizer may be performed by hot mixing. Hot mixing may be performed at a temperature of 290 to 330 °C. In addition, it can be carried out in a non-oxidizing atmosphere to achieve a high degree of polymerization while preventing the oxidative crosslinking reaction. The oxygen concentration of the gas phase in the non-oxidizing atmosphere may be less than 5% by volume or less than 2% by volume, and more specifically, the gas phase may be substantially free of oxygen. In the case of post-processing through high-temperature mixing, iodine that may be partially present at the terminal of the first polyarylene sulfide resin is sufficiently removed and the crystallinity is excellent to reduce shrinkage, so the post-processed first polyarylene sulfide is used to The dimensional stability of the final manufactured article can be improved.

In addition, high-temperature mixing may be performed under a reactor capable of heating and stirring. For example, the reactor may be a reactor of various materials such as SUS. The high-temperature mixing may be performed in a twin screw extruder, and the diameter ratio (L/D) of the twin screw extruder may be about 30 to 50. For example, the first polyarylene sulfide resin may be introduced through the main inlet of the twin-screw extruder, and other polymer materials such as thermoplastic resins or thermoplastic elastomers, fillers, etc. are separately provided through the side feeder located on the side of the extruder. can be put in The position of the side inlet may be about 1/3 to 1/2 from the outlet side of the entire barrel of the extruder, and through this, the filler and the like can be prevented from being broken by rotation and friction by the extruder screw in the extruder. In addition, the first polyarylene sulfide resin may be mixed with other additives added in a small amount before being added to the main inlet.

On the other hand, the post-processed first polyarylene sulfide resin is mainly composed of arylene sulfide units, but is usually derived from the first sulfur compound of the raw material, and the units according to the disulfide bond represented by [-SS-] are also the main chain can be included in The structural formula of the final polyarylene sulfide resin including a unit according to a disulfide bond may have the form of a copolymer presented by Eastman (US Patent No. 47680000). The structural formula of the copolymer may be expressed as in Structural Formula 1 below.

[Structural formula 1] -(Ar-S)x-(Ar-S-S)y-

In the post-processed first polyarylene sulfide resin, when the sum of x corresponding to the arylene sulfide structure and y corresponding to the copolymer sulfide structure in Structural Formula 1 is 1, the content of x is 0.900 to 0.999, 0.950 to 0.999 or 0.990 to 0.999. In addition, the disulfide bond fraction of the post-processed first polyarylene sulfide may be 0.001 to 10.0% by weight, specifically, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, or 0.7% by weight or more, and 10.0% by weight or less , 5.0 wt% or less, 2.0 wt% or less, 1.8 wt% or less, 1.6 wt% or less, 1.5 wt% or less, 1.4 wt% or less, 1.3 wt% or less, 1.2 wt% or less, 1.1 wt% or less, or 1 wt% or less can In the present specification, the fraction (wt%) of disulfide bonds may be defined as the difference between the theoretical amount of sulfur in polyarylene sulfide and the amount of sulfur measured by elemental analysis with respect to the theoretical amount of sulfur in polyarylene sulfide.

[Equation 1]

Disulfide bond fraction (wt%) = {(total weight of sulfur detected by elemental analysis) - (theoretical weight of sulfur in polyarylene sulfide)} / (theoretical weight of sulfur in polyarylene sulfide)

The post-processed first polyarylene sulfide resin may include iodine derived from a diiodo aromatic compound, and the content of iodine is 100 to 10,000 ppm based on the total weight of the post-processed first polyarylene sulfide resin, specifically , 250 ppm or more, 500 ppm or more, 750 ppm or more, 1,000 ppm or more, 1,250 ppm or more, or 1,500 ppm or more, and 9,000 ppm or less, 8,000 ppm or less, 7,000 ppm or less, 6,000 ppm or less, 5,000 ppm or less, 4,000 ppm or less, 3,000 ppm or less, 2,500 ppm or less, 2,250 ppm or less, 2,200 ppm or less, 2,100 ppm or less, 2,000 ppm or less, 1,900 ppm or less, or 1,800 ppm or less.

The post-processed first polyarylene sulfide resin has a melt viscosity of 1 Pa·s or more, 10 Pa·s or more, 50 Pa·s or more, 100 Pa·s or more, 500 Pa·s or more, 1,000 Pa·s or more, 1,500 Pa s or more, 1,700 Pa s or more, 1,800 Pa s or more, 1,900 Pa s or more, 2,000 Pa s or more, 2,100 Pa s or more, or 2,100 Pa s or more, and may be 7,000 Pa s or less; It may be 5,000 Pa·s or less, 4,000 Pa·s or less, 3,000 Pa·s or less, 2,500 Pa·s or less, 2,300 Pa·s or less, or 2,000 Pa·s or less. In the present specification, the melt viscosity is measured at 300° C. with a rotating disk viscometer, and when the viscosity is measured in an angular frequency section of 0.6 to 500 rad/s by a frequency sweep method, the viscosity at an angular frequency of 1.84 rad/s can be defined as

In addition, the non-linearity index may be 0.001 or more, 0.01 or more, 0.05 or more, 0.09 or more, or 0.10 or more, and 0.50 or less, 0.40 or less, 0.30 or less, 0.20 or less, 0,15 or less, 0.14 or less, 0.13 or less, 0.12 or less, 0.11 or less or 0.10 or less. By adjusting the nonlinearity index within this range, the post-processed polyarylene sulfide resin can have improved processability and good cavity balance. The non-linearity index may be an index regarding the molecular weight of the measurement target or molecular structure such as linear, branched, or crosslinked. Usually, when this value is close to 0, it indicates that the molecular structure of the resin is linear, and as this value increases, it indicates that many branched or crosslinked structures are included. In the present specification, the non-linearity index is measured at 300° C. with a rotating disk viscometer, and when the viscosity change rate in the shear rate section of ^{0.03 to 25 s −1 is measured by the frequency sweep method, it can be defined through Equation 2 below.}

[Equation 2]

Nonlinearity index = 1 - (melt viscosity at shear rate of ^{17.3 s -1} ) / (melt viscosity at shear rate of ^{3.22 s -1).}

The post-processed first polyarylene sulfide resin having a nonlinearity index in the above-described specific range is, for example, a method of solution polymerization of a mixture for melt polymerization including a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor. In the present invention, it is possible to obtain this polyarylene sulfide resin by making it high molecular weight to some extent.

The post-processed first polyarylene sulfide resin may have a branching index (α) of 0.10 or more, 0.20 or more, 0.30 or more, 0.40 or more, 0.50 or more, or 0.60 or more, and 1.00 or less, 0.90 or less, 0.80 or less, or 0.70 or less. In the present specification, α is calculated through the Mark-Howink equation represented by Equation 3 below. In general, the closer α is to 1, the more linear it is, and the closer it is to 0, the more it is a branched polymer.

[Equation 3]

[η] = KM ^α

In the above formula, η is an intrinsic viscosity, M is a weight average molecular weight, and K is a constant.

In addition, the post-processed first polyarylene sulfide resin may have a melting point of 250 to 300 °C, 260 to 300 °C, 265 to 300 °C, or 270 to 290 °C. In the present specification, the melting point is measured using a differential scanning calorimeter (DSC) from 30°C to 320°C at a rate of 10°C/min, cooled to 30°C, and then from 30°C to 320°C again. It may be measured while the temperature is raised at a rate of 10 °C / min.

The post-processed first polyarylene sulfide resin may have a crystallization temperature of 150 to 300 °C, 200 to 250 °C, 210 to 240 °C, 215 to 230 °C, or 216 to 225 °C. When the crystallization temperature is increased, not only the crystallization rate is increased, but also the crystallinity is affected, so that the mechanical properties of the final composition can be improved. In the present specification, the crystallization temperature is raised at a rate of 10°C/min from 30°C to 320°C using a differential scanning calorimeter differential scanning calorimeter, cooled to 30°C, and then again from 30°C to 320°C at a rate of 10°C/min. It may be measured while raising the temperature to

The molecular weight of the post-processed first polyarylene sulfide resin may be measured by weight average molecular weight, number average molecular weight, peak peak molecular weight, and the like. The weight average molecular weight of the post-processed first polyarylene sulfide resin is not particularly limited as long as the effects of the present invention are not impaired, but may be 25,000 g/mol or more, 30,000 g/mol or more, or 40,000 g/mol or more in terms of mechanical strength. and may be 100,000 g/mol or less, 80,000 g/mol or less, 65,000 g/mol or less, 50,000 g/mol or less, or 45,000 g/mol or less in terms of cavity balance. In addition, in order to achieve excellent mechanical strength and good cavity balance, the weight average molecular weight of the post-processed first polyarylene sulfide resin is set to 25,000 to 60,000 g/mol, 30,000 to 55,000 g/mol, 30,000 to 80,000 g/mol or 60,000. to 100,000 g/mol. In addition, the number average molecular weight may be 1,000 g/mol or more, 5,000 g/mol or more, 7,500 g/mol or more, 9,000 g/mol or more, 10,000 g/mol or more, or 12,000 g/mol or more, and 30,000 g/mol or less , 25,000 g/mol or less, 20,000 g/mol or less, 15,000 g/mol or less, 13,500 g/mol or less, or 13,000 g/mol or less. The peak peak molecular weight may be at least 10,000 g/mol, at least 15,000 g/mol, at least 20,000 g/mol, at least 25,000 g/mol, or at least 30,000 g/mol, and may be 140,000 g/mol or less, 100,000 g/mol or less, 75,000 or more. g/mol or less, 50,000 g/mol or less, 45,000 g/mol or less, 43,000 g/mol or less, 35,000 g/mol or less, or 30,000 g/mol or less.

The amount of outgas of the post-processed first polyarylene sulfide resin may be 0.001 to 0.50 wt%, 0.001 to 0.20 wt%, or 0.01 to 0.10 wt%. The amount of outgas in the present specification is the amount of gas generated when a sample of a predetermined amount of polyarylene sulfide resin or resin composition is heated at 330° C. for 20 minutes using a gas chromatograph (GC) mass spectrometer. it could be

The terminal of the post-processed first polyarylene sulfide resin may include a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, a sulfonate group, and the like. Specifically, it may include a functional group derived from a compound represented by one of Formulas 4 to 6 described above.

The first polyarylene sulfide resin post-processed with a compatibilizer has excellent compatibility with other resins and inorganic fillers having a hydrophilic functional group and/or a reactive group, so the amount of outgas may be lower than that of polyarylene sulfide resin that is not post-processed, and also , compared to a polyarylene sulfide resin prepared by using the same compound as a polymerization inhibitor during the polymerization of the resin, the addition amount of the polymerization inhibitor / compatibilizer, which can cause outgas, can be lowered and by-products can be minimized. , the amount of outgas may be low.

In addition, although not being bound by a particular theory, as the amount of outgas is reduced as described above, the polyarylene sulfide resin post-processed with a compatibilizer improves processability in the injection process, thereby improving the cavity balance and reducing the production cycle. effect can be shown.

In addition, the first polyarylene sulfide resin post-processed with a compatibilizer may have excellent mechanical strength, such as tensile strength, impact strength, and creep resistance, as compatibility is improved.

additive

Additives are not limited as long as they do not impair the effects of the present invention, but specifically, fibrous reinforcement, inorganic filler, antioxidant, stabilizer, processing heat stabilizer, plasticizer, mold release agent, colorant, lubricant (滑)劑), a weathering stabilizer, a foaming agent, a rust inhibitor, a wax, a nucleating agent, other resin components, an anti-drip agent, an additional compatibilizer, and the like.

The fibrous reinforcing material is, for example, glass fiber, PAN-based or pitch-based carbon fiber, silica fiber, silica alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, aluminum borate fiber, potassium titanate fiber, stainless steel, aluminum, titanium. , copper, and inorganic fibrous substances of metals such as pearls; and organic fibrous materials such as aramid fibers. Examples of the inorganic filler include silicates such as mica, talc, wollastonite, sericite, kaolin, clay, bentonite, asbesto, alumina silicate, zeolite, and pyrophyllite; carbonates such as calcium carbonate, magnesium carbonate, and dolomite; sulfates such as calcium sulfate and barium sulfate; metal oxides such as alumina, magnesium oxide, silica, zirconia, titania, and iron oxide; glass beads; glass flakes; ceramic beads; boron nitride; silicon carbide; calcium phosphate and the like. These fibrous reinforcing materials and inorganic fillers may be used individually or in mixture of 2 or more types.

Specifically, the glass fiber may be surface treated to improve interfacial adhesion with the resin, and the surface treatment may be performed using an epoxy and a silane having an amino group. For example, the glass fiber may be an alumino-borosilicate glass. In addition, the glass fibers may, for example, have an average diameter of 6 to 15 μm and an average length of 2 to 8 mm or 2 to 6 mm.

The heat stabilizer can be used to prevent the resin from decomposing due to the action of heat and light during the manufacturing process or use of the resin, and can be used in a high-temperature environment when mixing or molding polyarylene sulfide resin with other additives or resins. By minimizing the side reactions that occur, the physical properties of the final polyarylene sulfide resin composition can be improved. Heat stabilizer is calcium magnesium zinc-based heat stabilizer, calcium zinc-based heat stabilizer, organotin-based heat stabilizer, metal ore-based heat stabilizer, barium zinc-based heat stabilizer, epoxy zinc-based heat stabilizer, magnesium aluminum carbonate-based heat stabilizer, zinc-based heat stabilizer and a metal-based thermal stabilizer such as a lead-based thermal stabilizer, and a non-metallic thermal stabilizer such as an epoxy-based thermal stabilizer and an organic phosphite-based thermal stabilizer. A commercially available thermal stabilizer includes CLC-120 manufactured by Dubon, a magnesium aluminum carbonate-based thermal stabilizer.

In addition, as the heat stabilizer, for example, a primary phenolic stabilizer, a secondary phosphorus stabilizer, and a primary and secondary mixed stabilizer may be used, and both the primary and secondary stabilizers have a high molecular weight of the corresponding material or correspond to a residence at a high temperature. It is preferred that the material has good thermal stability. In this regard, preferred stabilizers include ADEKA's AO-60, AO-80, Chemtura's Ultanox627A, and Doverphos S9228.

In addition, the release agent may specifically be a silicone-based release agent, a wax-based release agent, a fluorine-based release agent, a surfactant-based release agent, or a mixed-type release agent. A commercially available release agent is Mitsui's Hi-Wax ^TM .

The nucleating agent may be used to accelerate the crystallization rate, and by using the nucleating agent, the degree of crystallinity can be increased even in a low-temperature mold to improve the surface properties of the resin. The nucleating agent may be an inorganic material having high temperature thermal stability, and may include talc, calcium silicate, silica, boron nitride, and the like. Specifically, boron nitride may be in the form of a hexagonal system, and purity of which is 0.5 wt % or less _{of B 2} O _{3 based on the total weight of boron nitride may be used.} Alternatively, boronitride having a purity of 95% by weight or more may be used.

In addition, other resins may be included in an appropriate amount according to the properties required for the first polyarylene sulfide resin. Here, the resin component is, for example, ethylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, (meth) of a monomer such as acrylonitrile. homopolymers or copolymers; polyesters such as polyurethane, polybutylene terephthalate, and polyethylene terephthalate; polyacetal; polycarbonate; polysulfone; polyallyl sulfone; polyethersulfone; polyphenylene ether; polyether ketone; polyether ether ketone; polyimide; polyamideimide; polyetherimide; silicone resin; epoxy resin; phenoxy resin; liquid crystal polymer; polyaryl ether; It may be a homopolymer such as a random copolymer or block copolymer, a graft copolymer, and the like.

Specifically, other resin components may include an elastomer to improve impact strength, and the elastomer is a polyvinyl chloride-based elastomer, a polyolefin-based elastomer, a polyurethane-based elastomer, a polyester-based elastomer, a polyamide-based elastomer, and a polybutadiene-based elastomer. and a terpolymer of glycidyl methacrylate and methyl acrylic ester.

In addition, the other resin component may include a thermoplastic elastomer (TPE). Thermoplastic elastomers are specifically thermoplastic polyether block amides (TPA), thermoplastic polyurethane elastomers (TPU), thermoplastic copolyester elastomers (TPC), styrene block copolymer based thermoplastic elastomers (TPS), thermoplastics and vulcanization. It may be a thermoplastic elastomer (TPV) made of an elastomer, or the like. The thermoplastic elastomer may be an epoxy elastomer comprising an epoxy functional group, such as a copolymer of ethylene and glycidyl methacrylate. A commercially available thermoplastic elastomer is Sumimoto's IGETABOND ^® BF-E.

The anti-drip agent may be used to prevent dripping when the polyarylene sulfide resin composition is burned. The anti-drip agent may include a fluorine-based anti-drip agent. Specifically, the anti-drip agent is a fluorine-based resin (polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, etc.), perfluoroalkanesulfonic acid alkali metal salt compound (perfluoromethanesulfonic acid sodium salt, perfluoro -n-butanesulfonate potassium salt, perfluoro-t-butanesulfonic acid potassium salt, perfluorooctanesulfonate sodium salt, perfluoro-2-ethylhexanesulfonate calcium salt, etc.), perfluoroalkanesulfonate It may include an alkaline earth metal salt of phonic acid, and more specifically, it may include polytetrafluoroethylene. Commercially available anti-drip agents include Hannanotech's FS-100, FS-200, and FS-300.

The additional compatibilizer means a compatibilizer additionally included in the polyarylene sulfide resin composition in addition to the compatibilizer used for post-processing the first polyarylene sulfide resin. Specifically, the additional compatibilizer may be a compatibilizer other than the compound represented by one of Formulas 4 to 6. For example, the additional compatibilizer may be an epoxy silane-based compatibilizer, and commercially available additional compatibilizers include Silquest ^® A-186 and A-187 from Momentive Performance Materials.

In addition, the metallic additive can promote the compatibilization reaction between the polyarylene sulfide resin and the thermoplastic elastomer, especially when used with a thermoplastic elastomer. Zinc salt, magnesium salt, calcium salt, sodium salt, lithium salt, etc. can be used as these metallic additives, and it is thermally stable and helps the reaction between the glycidyl functional group of the elastomer and the compatible functional group of the polyarylene sulfide resin. It is desirable to be able to give Preferred metallic additives meeting this requirement include zinc stearate (Sigma Aldrich-307564), calcium stearate (Sigma Aldrich-26411), magnesium acetate (Sigma Aldrich-228648), magnesium stearate (Sigma Aldrich). -415057), sodium stearate (Sigma-Aldrich-S3381), and lithium carbonate (Sigma-Aldrich-203629).

The additive may specifically include at least one selected from the group consisting of a fibrous reinforcement, a heat stabilizer, an elastomer, a release agent, an anti-drip agent, an additional compatibilizer, and a metallic additive, and specifically, the additive may include a heat stabilizer . More specifically, the additives may include glass fibers, and may include elastomers and metallic additives.

Post-processed first polyarylene sulfide resin composition

The resin composition for water section parts may include the post-processed first polyarylene sulfide resin and additives.

Specifically, the post-processed first polyarylene sulfide resin composition contains 0.1 wt% or more, 1 wt% or more of the post-processed first polyarylene sulfide resin based on the total weight of the post-processed first polyarylene sulfide resin composition , 2% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, or 60% by weight or more; , 99.9 wt% or less, 99 wt% or less, 98 wt% or less, 95 wt% or less, 90 wt% or less, 85 wt% or less, 80 wt% or less, 75 wt% or less, 70 wt% or less, or 65 wt% or less can be included as

On the other hand, the post-processed first polyarylene sulfide resin composition, based on the total weight of the post-processed first polyarylene sulfide resin composition, 0.01 wt% or more, 0.1 wt% or more, 1 wt% or more, 5 wt% or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 45% by weight or less or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 15% by weight or less.

More specifically, the post-processed first polyarylene sulfide resin composition contains 10 to 70 wt%, 10 to 60 wt%, 10 to 50 wt% of glass fibers based on the total weight of the post-processed first polyarylene sulfide resin composition. weight percent, 15 to 45 weight percent, 20 to 40 weight percent, or 25 to 35 weight percent, and 0.1 to 20 weight percent, 1 to 20 weight percent, 5 to 15 weight percent, or 7 to 7 weight percent elastomer. It may be included in an amount of 10% by weight. In addition, on the same basis, additional compatibilizers, metallic additives, mold release agents, anti-drip agents, and heat stabilizers may each independently include 0.01 to 5 wt%, 0.01 to 2 wt%, or 0.05 to 1 wt%.

In addition, the post-processed first polyarylene sulfide resin composition may contain 10 to 70% by weight of glass fibers based on the total weight of the post-processed first polyarylene sulfide resin composition, or 0.1 to 0.1 to each of an elastomer and a heat stabilizer 20% by weight and may be included in an amount of 0.01 to 5% by weight.

The post-processed first polyarylene sulfide resin composition has a small amount of outgas, and excellent tensile strength, impact strength and creep resistance, compared to the first polyarylene sulfide resin composition that is not post-processed with a compatibilizer. .

[Polyarylene Sulfide Mixed Resin Composition]

According to an embodiment, a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound; and an additive, a resin composition for water section parts (hereinafter, polyarylene sulfide mixed resin composition) is provided.

According to another embodiment, preparing a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; preparing a second polyarylene sulfide resin in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized; and an additive, and mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin.

The first polyarylene sulfide resin and additives are the same as described above.

Second polyarylene sulfide resin

The second polyarylene sulfide resin may be prepared by solution polymerization of a dihalo aromatic compound and a second sulfur compound.

The second polyarylene sulfide resin is not particularly limited as long as it is prepared including a step of solution polymerization of a dihalo aromatic compound and a second sulfur compound. As a commercial method for preparing such a polyarylene sulfide resin, a macallum process of solution polymerization of p-dichlorobenzene and sodium sulfide in the presence of a polar organic solvent such as N-methyl pyrrolidone (macallum process) This is known A typical process is described in US Pat. No. 2,513,188.

The melt polymerization may be performed in the presence of an organic polar solvent. The organic polar solvent is, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, caprolactam. , N-propylcaprolactam, N-methylcaprolactam, N-cyclohexylcaprolactam, N-methyl-2-pyrrolinone, N-ethyl-2-pyrrolidinone, N-isopropyl-2-pyrrolidinone , N-Isobutyl-2-pyrrolidinone, N-propyl-2-pyrrolidinone, N-butyl-2-pyrrolidinone, N-cyclohexyl-2-pyrrolidinone, N-methyl-3-methyl -2-pyrrolidinone, N-cyclohexyl-2-pyrrolidinone, N-methyl-2-piperidone, N-methyl-2-oxo-hexamethyleneimine, N-ethyl-2-oxo-hexamethyleneimine , hexamethyl phosphate triamide, hexaethyl phosphate triamide, tetramethyl urea, 1,3-dimethylethylene urea, 1,3-dimethylethylene urea, 1,3-dimethylpropylene urea, 1-methyl-1-oxosulfolane , 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, 1-methyl-1-oxophosphane, 1-propyl-1-oxophosphane and 1-phenyl-1-oxophosphane It may be at least one selected from the group consisting of. The organic polar solvent may be, for example, N-methylpyrrolidone.

The dihalo aromatic compound refers to a compound having an aromatic ring and two halo groups directly bonded thereto. Here, the halogen atom of the halo group may be each atom of fluorine, chlorine, bromine and iodine, and the two halo groups present in the dihalo aromatic compound may be the same or different from each other. More specifically, both halogen atoms may be chlorine. Dihalo aromatic compounds include, for example, o-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene, dihalonaphthalene, methoxy-dihalobenzene, dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl It may be at least one selected from the group consisting of ether, dihalodiphenylsulfone, dihalodiphenylsulfoxide and dihalodiphenylketone. The dihalo aromatic compound may be, for example, 1,4-dichlorobenzene, but is not particularly limited thereto.

The second sulfur compound may be at least one selected from the group consisting of an alkali metal sulfide and an alkali metal sulfide-forming compound capable of forming the alkali metal sulfide. In addition, the second sulfur compound may be at least one selected from the group consisting of alkali metal hydrosulfide and the alkali metal hydrosulfide-forming compound. The second sulfur compound includes, for example, alkali metal hydrosulfides such as lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide and cesium hydrosulfide, and alkali metal hydrosulfides such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide and cesium sulfide. It may be a metal sulfide, but is not particularly limited thereto. The alkali metal sulfide-forming compound or the alkali metal hydrosulfide-forming compound may be, for example, hydrogen sulfide. By blowing hydrogen sulfide into an alkali metal hydroxide (eg NaOH), alkali metal hydrosulfide (eg NaSH) or alkali metal sulfide (eg Na ₂ S) can be formed. The second sulfur compound may be at least one selected from the group consisting of anhydrides, hydrates, and aqueous solutions. The second sulfur compound may be, for example, sodium sulfide hydrate, but is not particularly limited thereto.

Polyarylene sulfide mixed resin composition

The resin composition for water section parts may include the first polyarylene sulfide resin, the second polyarylene sulfide resin, and an additive.

The solution-polymerized polyarylene sulfide resin, which is prepared by solution polymerization of a dihalo aromatic compound and a sulfur compound, has excellent physical properties such as a high crystallization temperature and mechanical strength, but is out due to the use of a solvent that can cause outgas It has a disadvantage in that the amount of gas is high, and thus the cavity balance is low. On the other hand, the melt-polymerized polyarylene sulfide resin, which is prepared by melt polymerization of a mixture containing a diiodo aromatic compound, a sulfur compound, and a polymerization inhibitor, has a remarkably low amount of outgas, but a disulfide bond with a weak structure due to the manufacturing process characteristics. It has a disadvantage in that mechanical strength is low as it is included.

However, the present inventors surprisingly found that by mixing the solution-polymerized polyarylene sulfide resin and the melt-polymerized polyarylene sulfide resin, the amount of outgas is low at a level comparable to that of the melt-polymerized polyarylene sulfide resin, and the cavity balance is excellent while , found that a polyarylene sulfide mixed resin composition having mechanical properties such as impact strength and creep resistance comparable to or superior to that of solution-polymerized polyarylene sulfide resin can be prepared.

The effect of the mixed resin composition is not limited to a specific theory, but may be achieved by the reaction of the first polyarylene sulfide resin and the second polyarylene sulfide resin. Specifically, when the first polyarylene sulfide resin and the second polyarylene sulfide resin are mixed, the disulfide bond of the first polyarylene sulfide resin is cleaved to further react with the halogen at the terminal of the second polyarylene sulfide. can do. Therefore, the disulfide bond, which is a weak structure of the first polyarylene sulfide, is removed and the molecular weight increases, and at the same time, the halogen of the second polyarylene sulfide can be additionally removed, so that not only mechanical properties are improved but also the amount of outgas This can be significantly reduced.

Mixing of the first polyarylene sulfide resin, the second polyarylene sulfide resin, and the additive may be performed through melt mixing. Melt mixing may be performed under any conditions as long as the first polyarylene sulfide resin and the second polyarylene sulfide resin can be melted. For example, melt mixing may be performed in a single-screw or twin-screw kneader extruder, a polymerization reactor, a kneader reactor, and the like. More specifically, melt mixing may be performed in a twin screw extruder, and may be performed at a temperature of 280 to 330°C, preferably 290 to 310°C. In this case, the discharge amount of the resin component may be 5 to 50 kg/hr at a rotation speed of 250 rpm, and may be adjusted to 20 to 35 kg/hr in consideration of dispersibility. It is preferable that the ratio (discharge amount/screw rotation speed) of the discharge amount (kg/hr) of a resin component and the screw rotation speed (rpm) is especially 0.08-0.14 kg/hr*rpm. During the mixing, by degassing in a reactor equipped with a vacuum line, a polyarylene sulfide mixed resin with a further reduced amount of outgas can be prepared.

The polyarylene sulfide mixed resin composition contains the first polyarylene sulfide resin in 0.1 wt% or more, 1 wt% or more, 2 wt% or more, 5 wt% or more, based on the total weight of the polyarylene sulfide mixed resin composition, 10 It may include at least 15 wt%, at least 15 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 60 wt%, or at least 70 wt%, 99.9 % by weight or less, 99% by weight or less, 98% by weight or less, 95% by weight or less, 90% by weight or less, 89% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less Weight % or less, 60 wt% or less, or 55 wt% or less may be included.

In addition, the polyarylene sulfide mixed resin composition contains the second polyarylene sulfide resin in an amount of 0.1 wt% or more, 1 wt% or more, 2 wt% or more, 5 wt% or more, based on the total weight of the polyarylene sulfide mixed resin composition. , 10% by weight or more, 15% by weight or more, or 20% by weight or more, 99.9% by weight or less, 99% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less , 60% by weight or less, 50% by weight or less, 49% by weight or less, 45% by weight or less, 40% by weight or less, 30% by weight or less, 25% by weight or less, or 20% by weight or less.

In addition, the polyarylene sulfide mixed resin composition may include 10 to 99.9 wt% of the first polyarylene sulfide resin and the second polyarylene sulfide resin based on the total weight of the polyarylene sulfide mixed resin composition, More specifically, it may be included in an amount of 20 to 99% by weight, 30 to 99% by weight, 30 to 95% by weight, 30 to 70% by weight, or 50 to 70% by weight.

The polyarylene sulfide mixed resin composition contains the second polyarylene sulfide resin in an amount of 30% by weight or less, specifically 0.0001 to 30% by weight based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin. It may be included in weight %. When the second polyarylene sulfide resin is included in the above range, the effect of mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin becomes significant, the amount of outgas decreases, and the cavity balance, tensile strength, and tensile strength Elongation, impact strength and creep resistance can be improved.

In addition, the polyarylene sulfide mixed resin composition contains an additive in an amount of 0.01 wt% or more, 0.1 wt% or more, 1 wt% or more, 5 wt% or more, 10 wt% or more, based on the total weight of the polyarylene sulfide mixed resin composition, 20% by weight or more or 30% by weight or more, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 45% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 15% by weight or less may be included.

More specifically, the polyarylene sulfide mixed resin composition contains 10 to 70% by weight, 10 to 60% by weight, 10 to 50% by weight, 15 to 45% by weight of glass fibers, based on the total weight of the polyarylene sulfide mixed resin composition. weight percent, 20 to 40 weight percent, or 25 to 35 weight percent, and 0.1 to 20 weight percent, 1 to 20 weight percent, 5 to 15 weight percent, or 7 to 10 weight percent elastomer. can In addition, on the same basis, additional compatibilizers, metallic additives, mold release agents, anti-drip agents, and heat stabilizers may each independently include 0.01 to 5 wt%, 0.01 to 2 wt%, or 0.05 to 1 wt%.

In addition, the polyarylene sulfide mixed resin composition contains 10 to 70% by weight of glass fibers based on the total weight of the polyarylene sulfide mixed resin composition, or 0.1 to 20% by weight and 0.01 to 20% by weight of an elastomer and a heat stabilizer, respectively It may be included in 5% by weight.

On the other hand, the polyarylene sulfide mixed resin means a resin composed of the first polyarylene sulfide and the second polyarylene sulfide, and the melt viscosity, non-linearity index, branching index (α), molecular weight of the polyarylene sulfide mixed resin And the melting point is the same as described above for the post-processed first polyarylene sulfide resin.

In addition, the polyarylene sulfide mixed resin may have a disulfide bond fraction of 0.001 to 10.0% by weight, specifically, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, or 1.0% by weight or more, and 10.0 Weight % or less, 5.0 wt% or less, 2.0 wt% or less, 1.8 wt% or less, or 1.6 wt% or less.

The polyarylene sulfide mixed resin may include iodine derived from a diiodo aromatic compound, and the content of iodine is 1 to 10,000 ppm, specifically, 5 ppm or more, based on the total weight of the polyarylene sulfide mixed resin; 10 ppm or more, 20 ppm or more, 40 ppm or more, 100 ppm or more, 500 ppm or more, or 1,000 ppm or more, 9,000 ppm or less, 8,000 ppm or less, 7,000 ppm or less, 6,000 ppm or less, 5,000 ppm or less, 4,000 ppm or less, 3,000 ppm or less, 2,500 ppm or less, 2,300 ppm or less, 2,270 ppm or less, 2,200 ppm or less, 2,000 ppm or less, 1,900 ppm or less, or 1800 ppm or less.

The crystallization temperature of the polyarylene sulfide mixed resin may be as high as that of the second polyarylene sulfide resin. For example, the polyarylene sulfide mixed resin may have a crystallization temperature of 150 to 300 °C, 200 to 280 °C, 210 to 260 °C, 210 to 270 °C, 220 to 260 °C, 225 to 255 °C, or 230 to 250 °C. When the crystallization temperature of the polyarylene sulfide mixed resin is increased, the crystallization rate is increased and the crystallinity is also affected, so that the mechanical properties of the final composition including the resin can be improved.

The amount of outgas of the polyarylene sulfide mixed resin may be 0.001 to 5% by weight, and specifically, 0.001% by weight or more, 0.01% by weight or more, 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, or 0.35% by weight or more. % or more, 3 wt% or less, 2 wt% or less, 1.5 wt% or less, 1.4 wt% or less, 1.35 wt% or less, 1.3 wt% or less, 1.2 wt% or less, 1.1 wt% or less, 1 wt% or less, It may be 0.8 wt% or less or 0.6 wt% or less.

The polyarylene sulfide mixed resin composition has a low outgas amount comparable to that of the first polyarylene sulfide resin composition and has excellent cavity balance, and has a tensile strength comparable to or superior to that of the second polyarylene sulfide resin composition; It may have tensile elongation, impact strength, creep resistance, and the like.

[Post-processed polyarylene sulfide mixed resin composition]

According to the embodiment, the first polyarylene sulfide resin is post-processed in which terminal groups derived from a compatibilizer are introduced into the first polyarylene sulfide resin in which the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor are melt-polymerized; a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound; And, comprising an additive, a resin composition for water section parts is provided.

According to another embodiment, preparing a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; preparing a second polyarylene sulfide resin in which a dihalo aromatic compound and a second sulfur compound are solution-polymerized; mixing an additive, the first polyarylene sulfide resin and the second polyarylene sulfide resin; and post-processing the first polyarylene sulfide resin using a compatibilizer.

The post-processed first polyarylene sulfide resin, second polyarylene sulfide resin, and additives are the same as described above.

Post-processed polyarylene sulfide mixed resin composition

The resin composition for water section parts may include the post-processed first polyarylene sulfide resin, the second polyarylene sulfide resin, and additives (hereinafter, post-processed polyarylene sulfide mixed resin composition). Their mixing is as described above.

However, post-processing of the first polyarylene sulfide resin may be performed before mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin, may be performed with mixing, or may be performed after mixing have. In addition, it may be performed before mixing and may be further performed with or after mixing, and other combinations are possible without limitation. For example, post-processing of the first polyarylene sulfide resin is performed by adding a compatibilizer to the twin-screw extruder when the first polyarylene sulfide resin and the second polyarylene sulfide resin are put into a twin-screw extruder and melt-mixed. can At this time, conditions can be set so that the ratio (discharge amount/screw rotation speed) of the discharge amount (kg/hr) of the resin component and the screw rotation speed (rpm) of a twin screw extruder becomes 0.02-0.2 kg/hr·rpm.

The terminal of the post-processed polyarylene sulfide mixed resin may include a functional group such as a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group.

The post-processed polyarylene sulfide mixed resin composition comprises 0.1% by weight or more, 1% by weight or more, 2% by weight or more, based on the total weight of the post-processed first polyarylene sulfide resin, based on the total weight of the post-processed polyarylene sulfide mixed resin composition; 5 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, 30 wt% or more, 40 wt% or more, 45 wt% or more, 50 wt% or more, 60 wt% or more, or 70 wt% or more 99.9 wt% or less, 99 wt% or less, 98 wt% or less, 95 wt% or less, 90 wt% or less, 89 wt% or less, 85 wt% or less, 80 wt% or less, 75 wt% or less, 70% by weight or less, 65% by weight or less, or 60% by weight or less.

In addition, the post-processed polyarylene sulfide mixed resin composition is 0.1 wt% or more, 1 wt% or more, 2 wt% or more, based on the total weight of the post-processed polyarylene sulfide mixed resin composition of the second polyarylene sulfide resin; 5% by weight or more, 10% by weight or more, 15% by weight or more, or 20% by weight or more, 99.9% by weight or less, 99% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 49% by weight or less, 45% by weight or less, 40% by weight or less, 30% by weight or less, 25% by weight or less, or 20% by weight or less.

In addition, the post-processed polyarylene sulfide mixed resin composition contains 10 to 99.9% by weight of the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin, based on the total weight of the post-processed polyarylene sulfide mixed resin composition. and, more specifically, 20 to 99% by weight, 30 to 99% by weight, 30 to 95% by weight, 30 to 70% by weight, or 50 to 70% by weight.

The post-processed polyarylene sulfide mixed resin composition contains the second polyarylene sulfide resin in an amount of 30% by weight or less, based on the total weight of the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin, specifically as 0.0001 to 30% by weight. When the second polyarylene sulfide resin is included in the above range, the effect of mixing the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin becomes significant, the amount of outgas decreases, cavity balance, and tensile strength , tensile elongation, impact strength and creep resistance can be improved.

In addition, the post-processed polyarylene sulfide mixed resin composition contains an additive of 0.01 wt% or more, 0.1 wt% or more, 1 wt% or more, 5 wt% or more, based on the total weight of the post-processed polyarylene sulfide mixed resin composition It may contain at least 20 wt%, or at least 30 wt%, 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, 50 wt% or less, 45 wt% or less, 40 wt% or more, 20 wt% or more, or 30 wt% or more Weight % or less, 30 wt% or less, 20 wt% or less, or 15 wt% or less may be included.

More specifically, the post-processed polyarylene sulfide mixed resin composition contains 10 to 70 wt%, 10 to 60 wt%, 10 to 50 wt% of glass fibers based on the total weight of the post-processed polyarylene sulfide mixed resin composition. , 15 to 45 wt%, 20 to 40 wt%, or 25 to 35 wt% of the elastomer, 0.1 to 20 wt%, 1 to 20 wt%, 5 to 15 wt%, or 7 to 10 wt% % can be included. In addition, on the same basis, additional compatibilizers, metallic additives, mold release agents, anti-drip agents, and heat stabilizers may each independently include 0.01 to 5 wt%, 0.01 to 2 wt%, or 0.05 to 1 wt%.

In addition, the post-processed polyarylene sulfide mixed resin composition contains 10 to 70% by weight of glass fibers based on the total weight of the post-processed polyarylene sulfide mixed resin composition, or 0.1 to 20% by weight of an elastomer and a heat stabilizer, respectively % and may be included in an amount of 0.01 to 5% by weight.

On the other hand, the post-processed polyarylene sulfide mixed resin means a resin composed of the post-processed first polyarylene sulfide and the second polyarylene sulfide, and the melt viscosity, non-linearity index, and branching of the post-processed polyarylene sulfide mixed resin Index (α), molecular weight, melting point, disulfide bond fraction, iodine content, crystallization temperature and outgas amount are the same as described above for the polyarylene sulfide mixed resin.

The post-processed polyarylene sulfide mixed resin composition has a low outgas amount comparable to that of the first polyarylene sulfide resin composition and has excellent cavity balance, while the first polyarylene sulfide resin composition and the second polyarylene sulfide It can exhibit superior tensile strength, tensile elongation, impact strength and creep resistance than all of the resin compositions.

This effect is not limited to a specific theory, but may be achieved by the reaction of the first polyarylene sulfide resin and the second polyarylene sulfide resin. Specifically, when the first polyarylene sulfide resin and the second polyarylene sulfide resin are mixed, the disulfide bond of the first polyarylene sulfide resin is cleaved to further react with the halogen at the terminal of the second polyarylene sulfide. can do. Therefore, the disulfide bond, which is a weak structure of the first polyarylene sulfide, is removed and the molecular weight increases, and at the same time, the halogen of the second polyarylene sulfide can be additionally removed, so that not only mechanical properties are improved but also the amount of outgas This can be significantly reduced.

Furthermore, since the first polyarylene sulfide resin is post-processed using a compatibilizer, compatibility with other resins having hydrophilic functional groups and/or reactive groups, inorganic fillers, etc. is improved, and the mechanical properties of the final article manufactured using the mixed resin Strength can be improved and the amount of outgas generated by heating can be significantly reduced. In addition, the reaction efficiency of the compatibilizer is remarkably superior compared to the case where the same compound is added as a polymerization inhibitor during the polymerization of the resin, so that the content of functional groups remaining in the final resin can be maximized. The target content of functional groups to be introduced into the final resin can be achieved through the compatibilizer. Therefore, in the case of post-processing with a compatibilizer, the amount of outgas can be further increased by lowering the addition amount of the polymerization inhibitor / compatibilizer, which can cause outgas, and by minimizing the by-products that can be generated by the compatibilizer in the high temperature environment required for the polymerization reaction. reduced, and at the same time, compatibility is improved, so that not only the cavity balance is excellent, but also physical properties such as tensile strength, impact strength, and creep resistance can be improved.

[Water section parts]

According to one embodiment, there is provided a water section component comprising a resin composition for the water section component.

The resin composition for the water section component may include the above-described first polyarylene sulfide resin, post-processed first polyarylene sulfide resin, second polyarylene sulfide resin, polyarylene sulfide mixed resin, or post-processed polyarylene sulfide mixed resin. It may include a resin.

In addition, the water section part may be a molded article in which the resin composition for the water section part is molded. The resin composition for water section parts may be molded in various methods and shapes without limitation. Typically, the resin composition may be cut into pellets, and by supplying these pellets to a molding machine and melt molding, a molded article having a desired shape can be finally obtained. Melt molding may be, for example, injection molding, extrusion molding, compression molding, or the like, and specifically may be injection molding. The mold temperature during injection molding may be about 50° C. or more, 60° C. or more, or 80° C. or more in consideration of crystallization, and may be about 190° C. or less, 170° C. or less, or 160° C. or less in consideration of the deformation of the specimen. The molding may be in various forms such as films, sheets, fibers, and the like.

The water section part may refer to parts used in the water section, such as toilet-related parts, hot water heater-related parts, pump-related parts, and bathroom-related parts. The above-described resin composition for water section parts has impact resistance, creep resistance and/or cavity balance, and thus is suitable for water section use. In particular, since opening and closing parts such as valves and faucets are generally exposed to high stress, acidic or alkaline cleaners and environments prone to damage by hot water, the resin composition for water section parts of the present invention is suitable for such water section opening and closing parts use. It can be useful.

Specifically, the water section component may include a pipe for the fluid. Fluid piping includes pipes, lining pipes, box nuts, pipe fittings (elbows, headers, tees, reducers, joints, couplers, etc.), various valves, flow meters, etc. It may include various parts.

[Production Example]

1. First polyarylene sulfide resin

Preparation a1: Preparation of PPS a1

A thermocouple capable of measuring the internal temperature of the reactor and a vacuum line capable of filling nitrogen and applying a vacuum were attached to the 5 L reactor, and 5,240 g of paradiiodobenzene and 450 g of elemental sulfur were added to the reactor. After heating the composition in the reactor containing paradiiodobenzene and elemental sulfur to 180° C. to completely melt and mix it, starting from the initial reaction conditions of 220° C. and 350 torr pressure, the temperature is gradually increased and reduced, and the temperature is 300° C. And the polymerization reaction was carried out under the final reaction conditions of a pressure of 1 torr or less. When a sample of the polymerization product was taken and the molecular weight of the sample was measured by gel permeation chromatography, when the weight average molecular weight (Mw) of the polymerization product reached about 15,000 g/mol, diphenyl as a polymerization inhibitor was added to the reactor. 24 g of disulfide (Sigma-Aldrich-169021) was added and the reaction was carried out for 1 hour, then the reaction was further proceeded for 1 hour by gradually reducing the pressure to a pressure of 0.5 torr or less, and then the reaction was terminated, and the reaction was completed with a small strand PPS a1 was prepared as a first polyarylene sulfide resin by processing it into pellets using a cutter.

Preparation a2: Preparation of PPS a2

In the same manner as in Preparation Example a1, except that 4.5 g of 2,2'-dithiodibenzoic acid (Sigma-Aldrich-43761, purity of 95.0% or more) was used instead of 24 g of diphenyldisulfide as a polymerization inhibitor, the first polyaryl About 1,500 g of PPS a2 was prepared as a ren sulfide resin.

2. Second polyarylene sulfide resin

Preparation b: Preparation of PPS b

3,027 g of sodium sulfide pentahydrate and 5,400 g of NMP as a polar organic solvent were added to the reactor, and the temperature was raised to 200° C. under a nitrogen atmosphere to distill off the water-NMP mixture. Next, a solution in which 2,646 g of para-dichlorobenzene and 17.01 g of parachlorobenzoic acid were dissolved in 2,070 g of NMP was added to the reactor, and the polymerization reaction was carried out at 220 to 240° C. for 8 to 12 hours under a nitrogen atmosphere. After cooling the reactor, the polymerization product was taken out and filtered. The filtered cake was further washed with 2,880 g of NMP, and 10 L of ion-exchanged water was added to the cake containing NMP, which was then stirred in an autoclave at 200° C. for 10 minutes, followed by further filtration. The final filtered cake was dried at 130° C. for 3 hours to prepare PPS b as a second polyarylene sulfide resin.

3. Post-processed first polyarylene sulfide resin

Preparation c1: Preparation of PPS c1

99.7 parts by weight (1,496 g) of the first polyarylene sulfide resin (PPS a1) prepared according to Preparation Example a1 and 2,2'-dithiodibenzoic acid as a compatibilizer (Sigma-Aldrich-43761, purity 95.0% or more) 0.3 weight After putting the part (4.5 g) into a twin-screw kneading extruder, melt blending was performed at a temperature of 300°C. The melt-blended polyarylene sulfide resin was processed into pellets using a small strand cutter to prepare PPS c1 as a post-processed first polyarylene sulfide resin.

Preparation c2: Preparation of PPS c2

Except for using 0.3 parts by weight of 4,4'-dithiodianiline (Sigma-Aldrich-369462, purity 98% or more) instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer, it was carried out in the same manner as in Preparation c1 , PPS c2 was prepared as a post-processed first polyarylene sulfide resin.

Preparation c3: Preparation of PPS c3

As a compatibilizer, instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid, 0.3 parts by weight of bis(3-hydroxyphenyl) disulfide (TCI (Tokyo Chemical)-B3149, purity of 97.0% or more (GC)) was used, except that 0.3 parts by weight was used. In the same manner as in Example c1, PPS c3 was prepared as a post-processed first polyarylene sulfide resin.

Preparation c4: Preparation of PPS c4

As a compatibilizer, instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid, 0.3 parts by weight of bis(4-hydroxyphenyl) disulfide (TCI (Tokyo Chemical)-B3827, purity 98.0% or more (GC)) was used, except that 0.3 parts by weight was used. In the same manner as in Example c1, PPS c4 was prepared as a post-processed first polyarylene sulfide resin.

Preparation c5: Preparation of PPS c5

Preparation c1 except that 0.3 parts by weight of 3-(triethoxysilyl)propane-1-thiol (Power chemical (China) SiSiB-PC2310) was used instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer In the same manner as described above, PPS c5 was prepared as the post-processed first polyarylene sulfide resin.

Preparation c6: Preparation of PPS c6

As a compatibilizer, 0.3 parts by weight of 1,2-bis(3-(triethoxysilyl)propyl)disulfane (Power chemical (Chinese company) SiSiB-PC2200) was used instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid Except that, in the same manner as in Preparation Example c1, PPS c6 was prepared as a post-processed first polyarylene sulfide resin.

4. Polyarylene sulfide resin composition

The first polyarylene sulfide resin, the second polyarylene sulfide resin, and the post-processed first polyarylene sulfide resin prepared according to the above-described preparation example were mixed in a twin-screw kneading extruder (Toshiba Group) in the weight ratios shown in Tables 1 to 5 below. A polyarylene sulfide resin composition (composition prior to mixing of additives) was prepared by melt-kneading at 300° C. at 300° C. (manufactured by Kai Corporation, TEM-35B), and processing it into pellets using a small strand cutter. Thereafter, the polyarylene sulfide resin composition was uniformly mixed using a tumbler in the weight ratio shown in Tables 1 to 5 below together with glass fiber, elastomer, additional compatibilizer, mold release agent, anti-drip agent, heat stabilizer, and a twin-screw kneading extruder. After melt-kneading at 300° C. (manufactured by Toshiba Kikai Co., Ltd., TEM-35B), it was processed into pellets using a small strand cutter to prepare a polyarylene sulfide resin composition (composition after mixing with additives).

Specifically, PPS A1-1 to A2-2 as the first polyarylene sulfide resin composition, PPS B1 and B2 as the second polyarylene sulfide resin composition, and PPS C1-1 as the post-processed first polyarylene sulfide resin composition to C2-2, PPS D1-1 to D2-5 as a polyarylene sulfide mixed resin composition, and PPS E1-1 to E2-4 as a post-processed polyarylene sulfide mixed resin composition were obtained.

The glass fiber, elastomer, heat stabilizer, metallic additive, additional compatibilizer, release agent, and anti-drip agent are specifically shown in Table 6 below.

[Experimental example]

In the polyarylene sulfide resin composition prepared according to the preparation example, the melting point, crystallization temperature, melt viscosity, nonlinear index, molecular weight, branching index, disulfide bond fraction, outgas amount and iodine content were measured for the composition before mixing with additives The composition after mixing the additives was measured/evaluated by the following methods for outgas amount, cavity balance, tensile strength, tensile elongation, impact strength and creep resistance, and is shown in Tables 7 to 12 below.

(1) Melting point (Tm) and crystallization temperature (Tc)

Using TA instrument's Q20 model differential scanning calorimeter (DSC), the temperature was raised from 30°C to 320°C at a rate of 10°C/min, and after cooling to 30°C at a rate of 10°C/min, The melting point and the crystallization temperature were measured again while the temperature was raised from 30°C to 320°C at a rate of 10°C/min.

(2) melt viscosity (MV) and non-linearity index

Melt viscosity is, with a rotating disk viscometer, when the viscosity is measured in the frequency range of 0.6 to 500 rad/s by a frequency sweep method at 300° C., the viscosity at each frequency condition of 1.84 rad/s has been defined

The nonlinear index was calculated through Equation 2 below.

[Equation 2]

Nonlinearity 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 peak molecular weight (Mp)

The number average molecular weight, weight average molecular weight, and peak peak molecular weight of the polyarylene sulfide resin composition were measured by gel permeation chromatography under the following measurement conditions. For all molecular weight measurements, six types of monodisperse polystyrene were used for calibration.

[Gel Permeation Chromatography Measurement Conditions]

Device: Agilent PL-220

Column: Agilent, PLgel pore size 105 Å + 104 Å + 500 Å + 50 Å (4 columns)

Column temperature: 210°C

Solvent: 1-chloronaphthalene

Measurement method: triple system detector (RI, viscometer, light scatter 15° and 90°)

(4) branch ratio (α)

The branching index was defined as an α value calculated by applying the viscosity measured from the triple system detector to the Mark-Howink equation of Equation 3 below. The Mark Howink equation is a relationship between molecular weight and intrinsic viscosity of a polymer, and the branching index (α) indicates the degree of branching of the polymer. That is, the closer α is to 1, the more linear the polymer, and the closer to 0, the more branched the polymer is.

[Equation 3]

[η] = KХM ^α

In the above formula, η is an intrinsic viscosity, M is a weight average molecular weight, and K is a constant.

(5) fraction of disulfide bonds (-S-S-)

The binding fraction of disulfide was calculated through Equation 1 below.

[Equation 1]

Disulfide bond fraction (wt%) = {(total weight of sulfur detected by elemental analysis) - (theoretical weight of sulfur in polyarylene sulfide)} / (theoretical weight of sulfur in polyarylene sulfide)

(6) Outgas volume

Composition before mixing of additives: The amount of gas generated by heating a predetermined amount of a sample of the polyarylene sulfide resin composition at 330° C. for 20 minutes was quantified in weight % using a gas chromatograph (GC) mass spectrometer.

Composition after mixing of additives: A sample of a predetermined amount of polyarylene sulfide resin composition was heated at 325° C. for 15 minutes, and the amount of gas generated was quantified in weight % using a gas chromatograph (GC) mass spectrometer.

(7) Iodine content

The iodine content of the polyarylene sulfide resin composition was measured by ion chromatograph (IC) using IC (AQF) Thermo Scientific, ICS-2500 (Mitsubishi AQF-100).

(8) Cavity balance

The polyarylene sulfide resin composition was injection molded using a washer mold having 40 cavities under the minimum molding conditions in which the cavity (C1) closest to the primary spool was completely filled. Molding conditions were set to a 75-ton molding machine, a cylinder temperature of 320°C, a mold temperature of 140°C, and no holding pressure. Among the cavities in the same runner as the cavity (C1), the filling degree (wt%) of the cavity (C10) furthest from the primary spool was calculated as the weight ratio of the molded part of the cavity (C1) to the molded part of the cavity (C1) . Since it can be said that the cavity balance is excellent as the filling degree of the cavity C10 is higher, the cavity balance of each polyarylene sulfide resin composition was evaluated based on the following criteria based on the filling degree.

AA: 90% by weight or more

A: 80% by weight or more and less than 90% by weight

B: 70% by weight or more and less than 80% by weight

C: 60% by weight or more and less than 70% by weight

D: less than 60% by weight

(9) Tensile strength and tensile elongation

The tensile strength and tensile elongation of the polyarylene sulfide resin composition were measured using Zwick's Z010 according to the ISO 527-2 method.

(10) Impact strength

Impact strength (unnotch): The polyarylene sulfide resin composition was processed to 80 mm (length) * 10 mm (width) * 4 mm (thickness), and its impact strength was measured by un-notched Charpy according to the ISO 179 method. Method was measured at room temperature.

Impact strength (notch): The polyarylene sulfide resin composition was processed to 80 mm (length) * 10 mm (width) * 4 mm (thickness), and its impact strength was measured by the notched Charpy method according to the ISO 179 method. Measured at room temperature.

(11) Creep resistance

A constant load (20 MPa) was applied to the polyarylene sulfide resin composition at 90° C., and flexural creep properties that change with time based on 1000 hours were observed.

Post-processed first polyarylene sulfide resin composition

As can be seen in the table above, PPS C1-1 to C1-8 containing the first polyarylene sulfide resin and additives post-processed with a compatibilizer include a first polyarylene sulfide resin and additives that are not post-processed with a compatibilizer. It was confirmed that the amount of outgas, impact strength and creep resistance were significantly superior to A1-2 including the first polyarylene sulfide resin and additive prepared by using PPS A1-1 and the compound of Formula 4 as a polymerization inhibitor. .

In addition, PPS C1-7 and C1-8 containing an elastomer as an additive together with the first polyarylene sulfide resin post-processed with a compatibilizer, PPS C1-1 to C1-6, PPS A1- containing no elastomer as an additive It was confirmed that the outgas amount, cavity balance, tensile elongation, and impact strength were all significantly superior to those of 1 and A1-2.

As can be seen in the table above, PPS C2-1 and C2-2 containing the first polyarylene sulfide resin and additives post-processed with a compatibilizer include a first polyarylene sulfide resin and additives that are not post-processed with a compatibilizer. It was confirmed that the tensile strength, tensile elongation, impact strength and creep resistance were all excellent compared to A2-2 containing the first polyarylene sulfide resin and additive prepared by using PPS A2-1 and the compound of Formula 4 as a polymerization inhibitor. could check

Polyarylene sulfide mixed resin composition

As can be seen from the above table, PPS D1-1 to D1-4, D1-6 and D1-7 comprising the first polyarylene sulfide resin, the second polyarylene sulfide resin and the additive are the first polyarylene Compared with PPS A1-1 containing a sulfide resin and additives, the impact strength and creep resistance were remarkably excellent while having the same or superior outgas amount and cavity balance.

On the other hand, PPS D1-1 to D1-4, D1-6 and D1-7, even compared to PPS B1 containing the second polyarylene sulfide resin and additives, equal or superior tensile strength or tensile elongation and creep resistance It was confirmed that it has remarkably excellent outgas amount, cavity balance and impact strength while having

Moreover, PPS D1-1 to D1-4, D1-6 and D1-7 are the contents of the second polyarylene sulfide resin based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin. The amount of outgas, cavity balance, impact strength and creep resistance were remarkably superior to that of PPS D1-5, which is more than 30% by weight.

As can be seen in the above table, the PPS D2-1, D2-2, D2-4 and D2-5 comprising the first polyarylene sulfide resin, the second polyarylene sulfide resin and the additive are the first polyarylene Compared with PPS A2-1 containing sulfide resin and additives, the outgas amount, tensile strength, tensile elongation, impact strength and creep resistance were all excellent while having the same or superior cavity balance.

In addition, PPS D2-1, D2-2, D2-4 and D2-5 were outgassed, cavity balance, tensile strength, tensile elongation, even compared with PPS B2 containing the second polyarylene sulfide resin and additive. , impact strength and creep resistance were all excellent.

Moreover, PPS D2-1, D2-2, D2-4 and D2-5 are the content of the second polyarylene sulfide resin based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin. Outgas amount, cavity balance, tensile strength, tensile elongation, impact strength and creep resistance were all excellent compared to PPS D2-3, which is more than 30% by weight.

In addition, PPS D2-1, D2-2 and D2-4, which additionally contain a heat stabilizer as an additive, have outgassing, tensile strength, tensile elongation and creep resistance compared to PPS D2-5 which does not contain a heat stabilizer. This excellence was confirmed.

Post-processed polyarylene sulfide mixed resin composition

As can be seen in the table above, PPS E1-1, E1-2, E1-4 to E1-12 including the post-processed first polyarylene sulfide resin, the second polyarylene sulfide resin and additives are the first poly When compared to both PPS A1-1 including arylene sulfide resin and additives and PPS B1 including second polyarylene sulfide resin and additives, outgas volume, cavity balance, impact strength and creep resistance are equal or significantly higher Excellent.

In addition, PPS E1-1, E1-2, E1-4 to E1-12 are outgas amount, cavity, even compared to PPS D1-2 including the first polyarylene sulfide resin, the second polyarylene sulfide resin and the additive. It was confirmed that the balance and impact strength were very good.

Moreover, PPS E1-1 and E1-2 are PPS E1- in which the content of the second polyarylene sulfide resin is greater than 30% by weight based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin. 3, the amount of outgas, cavity balance, tensile strength, tensile elongation, impact strength and creep resistance are all excellent, and PPS E1-4 to E1-12 also contain more than 30% by weight of the second polyarylene sulfide resin. It was confirmed that the cavity balance, tensile strength, tensile elongation, impact strength and creep resistance were all excellent compared to PPS E1-13 and E1-14.

As can be seen in the table above, the post-processed PPS E2-1, E2-2 and E2-4 including the first polyarylene sulfide resin, the second polyarylene sulfide resin and the additive are the first polyarylene sulfide resins. And when compared with both PPS A2-1 and PPS B2 containing the second polyarylene sulfide resin and additive, the amount of outgas, cavity balance, tensile strength, tensile elongation, impact strength and creep resistance are equal or remarkably superior.

In addition, PPS E2-1, E2-2 and E2-4 are outgas amount, cavity balance, tensile strength compared to PPS D2-1 including the first polyarylene sulfide resin, the second polyarylene sulfide resin and additives. , tensile elongation, impact strength and creep resistance were remarkably excellent.

Moreover, in PPS E2-1, E2-2 and E2-4, the content of the second polyarylene sulfide resin is greater than 30% by weight based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin. It was confirmed that the outgas amount, cavity balance, tensile strength, tensile elongation, impact strength and creep resistance were significantly superior to PPS E2-3.

Claims (19)

a first polyarylene sulfide resin in which a terminal group derived from a compatibilizer is introduced into a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; and
A resin composition for water section parts, comprising at least one additive selected from the group consisting of glass fiber, elastomer, mold release agent, anti-drip agent, metallic additive and heat stabilizer.
The method of claim 1,
The additive comprises the glass fiber, or comprises the elastomer and the heat stabilizer, a resin composition for water section parts.
The method of claim 1,
The compatibilizer comprises at least one functional group selected from the group consisting of a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group, the resin composition for water section parts.
The method of claim 1,
The compatibilizer is a compound represented by one of the following Chemical Formulas 4 to 6, a resin composition for water section parts:
[Formula 4]

In the above formula,
Y ¹ and Y ² are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ¹ , -SB ² , -COOB ³ , -NB ⁴ B ⁵ , -SO ₃ B ⁶ and -NHCOB ⁷ ,
B ¹ to B ⁷ 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 3 carbon atoms, and a substituted or unsubstituted phenyl group,
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,
p ¹ and p ² are each independently an integer of 1 to 3,
When Z ¹ ' and Z ² ' are alkenyl groups having 2 carbon atoms and are bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring,
When Z ³ ' and Z ⁴ ' are alkenyl groups having 2 carbon atoms and are bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring,
The substituted alkyl group of 1 or 2 carbon atoms or the substituted alkenyl group of 1 or 2 carbon atoms of ^{Z 1 '} to Z ^{4' has a substituent of an alkyl group or phenyl group of 1 or 2 carbon atoms,}
The ^{substituted alkyl group or substituted phenyl group having 1 to 3 carbon atoms of B 1} to B ^{7 has} a substituent of an alkyl group or phenyl group having 1 or 2 carbon atoms,
provided that at least one of ^{Y 1} and Y ² is selected from the group consisting ^{of -OB 1} , -SB ² , -COOB ³ , -NB ⁴ B ⁵ , -SO ₃ B ⁶ and -NHCOB ^{7 ;}
[Formula 5]

In the above formula,
Y ^{3 To} Y ⁶ are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ⁸ , -SB ⁹ , -COOB ¹⁰ , -NB ¹¹ B ¹² , -SO ₃ B ¹³ and -NHCOB ¹⁴ ,
B ⁸ to B ¹⁴ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation and an alkyl group having 1 to 3 carbon atoms,
R ¹ ' to R ⁴ ' are each independently an alkylene group and an alkoxy group having 1 to 5 carbon atoms,
provided that at least one of ^{Y 3} to Y ^{6 is —SB 9 in} which ^{B 9} is a hydrogen group;
[Formula 6]

In the above formula,
Y ⁷ to Y ¹² are each independently selected from the group consisting of a hydrogen group, a halo group, -OB ¹⁵ , -SB ¹⁶ , -COOB ¹⁷ , -NB ¹⁸ B ¹⁹ , -SO ₃ B ²⁰ and -NHCOB ²¹ ,
B ¹⁵ to B ²¹ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation and an alkyl group having 1 to 5 carbon atoms,
R ⁵ ′ and R ⁶ ′ are each independently an alkylene group having 1 to 5 carbon atoms.
The method of claim 1,
The first polyarylene sulfide resin is post-processed using the compatibilizer at a temperature of 280 to 330 ℃, a resin composition for water section parts.
The method of claim 1,
The amount of outgas of the post-processed first polyarylene sulfide resin is 0.001 to 0.20% by weight, or
The disulfide bond fraction of the post-processed first polyarylene sulfide resin is 0.1 to 2.0 wt%, a resin composition for water section parts.
a first polyarylene sulfide resin obtained by melt polymerization of a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor;
a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound; and
at least one additive selected from the group consisting of glass fibers, elastomers, mold release agents, anti-drip agents, metallic additives and heat stabilizers;
The second polyarylene sulfide resin is included in an amount of 0.0001 to 30% by weight based on the total weight of the first polyarylene sulfide resin and the second polyarylene sulfide resin, the resin composition for water section parts.
8. The method of claim 7,
The first polyarylene sulfide resin and the second polyarylene sulfide resin are melt-mixed at 280 to 330 ℃, a resin composition for water section parts.
8. The method of claim 7,
The additive comprises the glass fiber, or comprises the elastomer and the heat stabilizer, a resin composition for water section parts.
8. The method of claim 7,
Based on the total weight of the resin composition,
1 to 89% by weight of the first polyarylene sulfide resin,
1 to 45% by weight of the second polyarylene sulfide resin,
A resin composition for water section parts comprising the glass fiber in an amount of 10 to 70% by weight.
8. The method of claim 7,
Based on the total weight of the resin composition,
1 to 98% by weight of the first polyarylene sulfide resin,
1 to 49% by weight of the second polyarylene sulfide resin,
Containing the elastomer in an amount of 0.1 to 20% by weight,
A resin composition for water section parts comprising the heat stabilizer in an amount of 0.01 to 5% by weight.
8. The method of claim 7,
The polyarylene sulfide mixed resin composed of the first polyarylene sulfide resin and the second polyarylene sulfide resin has a crystallization temperature of 210 to 260° C., a resin composition for water section parts.
8. The method of claim 7,
The water section part, wherein the polyarylene sulfide mixed resin composed of the first polyarylene sulfide resin and the second polyarylene sulfide resin has an outgas amount of 0.01 to 1.40% by weight and a disulfide bond fraction of 0.1 to 2.0% by weight. for resin composition.
a post-processed first polyarylene sulfide resin in which an end group derived from a compatibilizer is introduced into a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized;
a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound; and
at least one additive selected from the group consisting of glass fibers, elastomers, mold release agents, anti-drip agents, metallic additives and heat stabilizers;
The second polyarylene sulfide resin is included in an amount of 0.0001 to 30% by weight based on the total weight of the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin, the resin composition for water section parts.
15. The method of claim 14,
The additive comprises the glass fiber, or comprises the elastomer and the heat stabilizer, a resin composition for water section parts.
15. The method of claim 14,
The polyarylene sulfide mixed resin composed of the first polyarylene sulfide resin and the second polyarylene sulfide resin has a crystallization temperature of 210 to 260° C., a resin composition for water section parts.
15. The method of claim 14,
The post-processed polyarylene sulfide mixed resin composed of the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin has an outgas amount of 0.01 to 1.40% by weight and a disulfide bond fraction of 0.1 to 2.0% by weight. , Resin composition for water section parts.
A water section part comprising a molded article in which the resin composition according to any one of claims 1 to 17 is molded.
A fluid piping comprising a molded article molded with the resin composition according to claim 1 .