KR20210105748A - Polyarylene sulfide resin and preparation method thereof - Google Patents

Abstract

An embodiment relates to a novel polyarylene sulfide resin and a method for manufacturing the same. The polyarylene sulfide resin of the embodiment has desirable properties such as a low outgas amount, good compatibility, and/or a low disulfide bond fraction, so that the polyarylene sulfide resin has excellent heat resistance, flame resistance, corrosion resistance, durability, mechanical strength, and the like.

Description

Polyarylene sulfide resin and manufacturing method thereof

Embodiments relate to polyarylene sulfide resins and methods for preparing the same.

Polyarylene sulfide is an important engineering plastic, and due to its high heat resistance, chemical resistance, nonflammability, high strength, and the like, the demand for polyarylene sulfide is increasing for various uses such as highly durable plastic molded products and electrical products.

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.

First, 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.

On the other hand, the polyphenylene sulfide resin produced 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. have

However, the polyphenylene sulfide resin produced by the melt polymerization method has low reactivity with processing additives due to the non-polar end group of the resin, so it is difficult to modify it to have desired properties, and there are limitations in its use or usage, and There is a limitation in that the disulfide bond derived from the sulfur compound acts as a weak structure in the resin and lacks mechanical properties.

US Patent No. 2,513,188

Under this background, as a result of intensive research, the present inventors not only increase the compatibility of the polyarylene sulfide resin but also further reduce the amount of outgas by post-processing the polyarylene sulfide resin with a compatibilizer, and solution polymerization The present invention was completed by discovering that the limitations of each polyarylene sulfide resin can be overcome by blending the polyarylene sulfide resin and the melt-polymerized polyarylene sulfide resin.

Accordingly, in the embodiments described below, it is an object to provide a novel polyarylene sulfide resin and a method for preparing the same.

According to one embodiment, a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; and a post-processed first polyarylene sulfide resin comprising a terminal group derived from a compatibilizer.

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; and a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound, a polyarylene sulfide mixed resin is provided.

According to another embodiment, a post-processed first polyaryl comprising a terminal group derived from a first polyarylene sulfide resin melt-polymerized with a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor and a compatibilizer. rensulfide resin; And a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound is mixed, and a post-processed polyarylene sulfide mixed resin 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; and post-processing the first polyarylene sulfide resin using a compatibilizer.

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 mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin.

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 in the presence of an organic polar solvent; mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin; and post-processing the first polyarylene sulfide resin using a compatibilizer.

Since the polyarylene sulfide resin of the embodiment has desirable properties such as low outgas amount, excellent compatibility and/or low disulfide bond fraction, it is excellent in heat resistance, flame resistance, corrosion resistance, durability, mechanical strength, and the like.

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]

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; and a post-processed first polyarylene sulfide resin comprising a terminal group derived from a compatibilizer.

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; 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 that 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 4, 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 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.

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 having 1 or 2 carbon atoms or a phenyl group.

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 .} In addition, 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 an alkylene group having 1 to 5 carbon atoms.

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.

[Formula 4]

X ¹³ is a hydrogen group, a halo group, an alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted phenyl group, -OA ²² , -SA ²³ , -COOA ²⁴ , NA ²⁵ A ²⁶ , -SO ₃ A ²⁷ and -NHCOA is selected from the group consisting of ^{28 , and A 22} to A ²⁸ are each independently a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted phenyl group from the group consisting of selected, W is a halo group, Z ⁵ and Z ⁶ are each independently 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 It is selected from the group, and n is an integer from 1 to 3.

When Z ⁵ and Z ⁶ 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 n is 2 or more, two or more X ¹³ bonded to one aromatic ring may be the same as or different from each other.

Z ⁵ and Z ⁶ may be bonded to two adjacent carbon atoms. Also, ^{at least one of Z 5} and Z ⁶ may not be a hydrogen group. In addition, at least one of ^{X 13} may be selected from the group consisting ^{of -OA 22} , -SA ²³ , -COOA ²⁴ , NA ²⁵ A ²⁶ , -SO ₃ A ²⁷ and -NHCOA ^{28 .}

The substituted phenyl group of X ¹³ may have a substituent of -SH or -SS-Ph. In addition, _{the substituted alkyl group having 1 to 3 carbon atoms or the substituted phenyl group of A 22} to A ₂₈ may have a substituent of an alkyl group or phenyl group having 1 or 2 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 it is possible to prepare a composition for melt polymerization in which a polymerization inhibitor is mixed in a mixture containing the first sulfur compound.

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.

In addition, the first polyarylene sulfide resin is a fibrous reinforcing material, an inorganic filler, an antioxidant, a stabilizer, a processing heat stabilizer, a plasticizer, a mold release agent, and a colorant in the range that does not impair the effects of the present invention. , lubricants, weathering stabilizers, foaming agents, rust inhibitors, waxes, nucleating agents, and other additives such as resin components may be further included.

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. In addition, when glass fiber is used, the glass fiber may be surface-treated to improve interfacial adhesion with the resin, and the surface treatment may be an alumino-borosilicate glass using a silane having an epoxy and an amino group. The glass fibers may have, for example, an average diameter of 6 to 15 μm and an average length of 2 to 5 mm.

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 the purity _{may be used with a B 2} O ₃ content of 0.5 wt % or less based on the total weight of boron nitride. 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. In addition, other resin components may include an elastomer to improve impact strength, and the elastomer includes a polyvinyl chloride-based elastomer, a polyolefin-based elastomer, a polyurethane-based elastomer, a polyester-based elastomer, a polyamide-based elastomer, a polybutadiene-based elastomer, and It may be selected from the group consisting of a terpolymer of glycidyl methacrylate and methyl acrylic ester.

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 phenol 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 5 to 8.

[Formula 5]

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 6]

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. an alkylene group, provided that at least one of ^{Y 3} to Y ⁶ is selected from the group consisting ^{of -OB 8} , -SB ⁹ , -COOB ¹⁰ , -NB ¹¹ B ¹² , -SO ₃ B ¹³ and -NHCOB ^{14 .} Here, at least one of ^{Y 3} to Y ⁶ may be ^{—SB 9 in which B 9} is a hydrogen group.

[Formula 7]

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.

[Formula 8]

Y ¹³ may be selected from the group consisting of a halo group, -OB ²² , -SB ²³ , -COOB ²⁴ , NB ²⁵ B ²⁶ , -SO ₃ B ²⁷ and -NHCOB ²⁸ , and B ₂₂ to B ₂₈ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted phenyl group, W' is a halo group, and Z ⁵ ' and Z ⁶ ' 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 q is an integer of 1 to 3.

When Z ⁵ ′ and Z ⁶ ′ are an alkenyl group 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 q is 2 or more, 2 or more Y ¹³ bonded to one aromatic ring may be the same as or different from each other.

Z ⁵ ′ and Z ⁶ ′ may be bonded to two adjacent carbon atoms. Also, ^{at least one of Z 5} ′ and Z ⁶ ′ may not be a hydrogen group. In addition, at least one of ^{Y 13} may be selected from the group consisting ^{of -OB 22} , -SB ²³ , -COOB ²⁴ , NB ²⁵ B ²⁶ , -SO ₃ B ²⁷ and -NHCOB ^{28 .}

The substituted alkyl group or substituted phenyl group having 1 or 2 carbon atoms of B ²² to B ²⁸ may have a substituent of an alkyl group or phenyl group having 1 or 2 carbon atoms.

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 phenol group, an amino group, an amide group, a silane group, a sulfide group, or a sulfonate group, so the terminal group derived from the compatibilizer may also be used. It may be a functional group such as a carboxyl group, a carboxylate group, a phenol group, an amino group, an amide group, a silane group, a sulfide group, or a sulfonate group.

More specifically, the terminal group derived from the compatibilizer may have a structure represented by one of Chemical Formulas 9 to 12 below.

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

In the above formula, Z ¹ ', Z ² ', Z ⁵ ', Z ⁶ ', Y ¹ to Y ⁵ , Y ⁷ to Y ⁹ , Y ¹³ , R ¹ ' to R ⁵ ', p ¹ and q are as described above. same.

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 and impact strength can be improved. In addition, the first polyarylene sulfide resin post-processed with a compatibilizer may exhibit the effect of reducing the production cycle as well as exhibiting excellent processability in the extrusion or injection process as the amount of outgas is reduced as described above.

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. In the non-oxidizing atmosphere, the oxygen concentration of the gas phase may be less than 5% by volume or less than 2% by volume, and more specifically, may contain substantially no oxygen in the gas phase. 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.

In addition, the post-processed first polyarylene sulfide resin may further include an additive within a range that does not impair the effects of the present invention, and the additive is as described above.

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 units according to disulfide bonds may have the form of a copolymer suggested by Eastman (US Patent No. 47,680,000). 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 copolymerized 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 to 250 ppm or more, 500 ppm or more, 750 ppm or more, or 900 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 or less, 2,000 ppm or less, or 1,500 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, or 1,800 Pa s or more, and may be 7,000 Pa s or less, 5,000 Pa s or less, 4,000 Pa s or less, 3,000 Pa s or less, 2,500 Pa s or less, or 2,000 It may be less than or equal to Pa·s. 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 nonlinearity index may be 0.001 or more, 0.01 or more, 0.05 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, 0.10 or less , 0.05 or less or 0.02 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 a shear rate of ^{17.3 s -1} ) / (melt viscosity at a 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 can be defined as the melting point measured while the temperature is raised at a rate of 10 °C / min.

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 or 30,000 g/mol or more in terms of mechanical strength, and the cavity balance of In terms of it, it may be 100,000 g/mol or less, 80,000 g/mol or less, 65,000 g/mol or less, or 55,000 g/mol or less. 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 12,000 g/mol or less. The peak peak molecular weight can be at least 10,000 g/mol, at least 15,000 g/mol, at least 20,000 g/mol, or at least 25,000 g/mol, and at most 140,000 g/mol, at most 100,000 g/mol, at most 75,000 g/mol, at most 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 320° C. for 30 minutes using a gas chromatograph (GC) mass spectrometer. it could be

The oligomer content of the post-processed first polyarylene sulfide resin may be 0.01 to 5 wt% based on the total weight of the post-processed first polyarylene sulfide resin, and specifically, 0.10 wt% or more, 0.50 wt% or more, or 1.00 wt% or more, 3.00 wt% or less, 2.00 wt% or less, 1.50 wt% or less, 1.40 wt% or less, 1.39 wt% or less, 1.38 wt% or less, 1.37 wt% or less, 1.36 wt% or less or 1.35 wt% may be below. In the present specification, the oligomer content may be calculated by weight % of the polymer having a molecular weight of 1,000 g/mol or less among the total peaks of the polyarylene sulfide resin shown in high-temperature gel-permeation chromatography.

When the oligomer content of the polyarylene sulfide resin is excessive, the oligomer acts as a defect when the polyarylene sulfide resin is extruded, and processability may be significantly reduced. Therefore, the oligomer content of the polyarylene sulfide resin is It is preferable to fall within the range. Moreover, when the oligomer content of the polyarylene sulfide resin is within the above range, the amount of outgas generated during processing is reduced, the single yarn rate can be lowered when used for fiber applications, and mechanical properties such as impact strength can also be improved. .

In addition, the post-processed first polyarylene sulfide resin may include inorganic materials such as Fe, Na, Ca, and Li, and the content of these inorganic materials is 0 to based on the total weight of the post-processed first polyarylene sulfide resin. may be 100 ppm, specifically, may be 1 ppm or more, 3 ppm or more, or 5 ppm or more, based on the total weight of the post-processed first polyarylene sulfide resin, and may be 50 ppm or less, 40 ppm or less, 30 ppm or less, or 20 ppm or less. In the present specification, the inorganic content may be one measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES) by heating and decomposing the resin with a mixed acid (nitric acid/perchloric acid/sulfuric acid) and then diluting it with ultrapure water. When the content of the inorganic material is high, the monofilament rate may increase when manufacturing fibers using the polyarylene sulfide resin, and it may cause short circuits in the manufacturing of electrical and electronic products. It is preferable to belong to In addition, when the inorganic material content of the polyarylene sulfide resin is within the above range, unnecessary side reactions can be suppressed during melt mixing.

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, and thus the amount of outgas may be lower than that of the non-post-processed polyarylene sulfide resin, 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.

[Polyarylene Sulfide Mixed Resin]

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; and a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound, a polyarylene sulfide mixed resin 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 mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin is provided.

The first polyarylene sulfide resin is 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 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

The polyarylene sulfide mixed resin may be a mixture of a melt-polymerized first polyarylene sulfide resin and a solution-polymerized second polyarylene sulfide resin.

The solution-polymerized polyarylene sulfide resin, which is prepared by solution polymerization of a dihalo aromatic compound and a sulfur compound in the presence of an organic polar solvent, has excellent physical properties such as high mechanical strength, but due to the use of a solvent that can cause outgas This has a disadvantage in that the amount of outgas is high. 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 solution-polymerized polyarylene sulfide resin The present invention was completed by discovering that a polyarylene sulfide mixed resin having better physical properties than that of an arylene sulfide resin can be prepared.

The effect of the mixed resin 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 and the second polyarylene sulfide resin 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 second polyarylene sulfide resin included in the polyarylene sulfide mixed resin is 0.001 to 1000 parts by weight, 0.01 to 100 parts by weight, 0.5 to 20 parts by weight, 0.1 to 10 parts by weight, based on 1 part by weight of the first polyarylene sulfide resin. parts by weight, 0.25 to 99 parts by weight, 0.25 to 4 parts by weight, 0.2 to 5 parts by weight, 0.4 to 3 parts by weight, 0.5 to 2 parts by weight, or 1.5 to 4 parts by weight, but is not particularly limited thereto.

The polyarylene sulfide mixed resin may include the first polyarylene sulfide resin in an amount of 0.1 to 99.9 parts by weight based on the total weight of the polyarylene sulfide mixed resin. In addition, the polyarylene sulfide mixed resin may include the second polyarylene sulfide resin in an amount of 0.1 to 99.9 parts by weight based on the total weight of the polyarylene sulfide mixed resin.

In addition, the polyarylene sulfide mixed resin contains 95% or more, 95.5% or more, 96% or more, 96.5% or more of the first polyarylene sulfide resin and the second polyarylene sulfide resin based on the total weight of the polyarylene sulfide mixed resin. % or more, 97% or more, 97.5% or more, 98% or more, 98.5% or more, 99% or more, 99.5% or more, or 99.9% or more.

In addition, the polyarylene sulfide mixed resin may further include an additive within a range that does not impair the effects of the present invention, and the additive is as described above.

In addition, the melting point, melt viscosity, molecular weight, nonlinearity index, and branching index of the polyarylene sulfide mixed resin are the same as those described above for the post-processed first polyarylene sulfide resin.

On the other hand, the polyarylene sulfide mixed resin may have a disulfide bond fraction of 0 to 10.0 wt%, specifically, 0.01 wt% or more, 0.01 wt% or more, 0.1 wt% or more, or 0.2 wt% or more, and 10.0 wt% 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 may be below. The polyarylene sulfide mixed resin may have a low disulfide bond fraction because disulfide bonds in the first polyarylene sulfide resin may be cleaved and removed due to mixing of the first polyarylene sulfide resin and the second polyarylene sulfide resin and, thereby, may improve mechanical properties.

The polyarylene sulfide mixed resin may have an outgas amount of 0.001 to 0.50% by weight, and more specifically, 0.01% by weight or more, 0.02% by weight or more, 0.03% by weight or more, or 0.04% by weight or more, 0.30% by weight or less, 0.20 wt% or less, 0.18 wt% or less, 0.16 wt% or less, 0.15 wt% or less, 0.14 wt% or less, 0.13 wt% or less, 0.12 wt% or less, or 0.11 wt% or less. Since the polyarylene sulfide mixed resin may have a reduced amount of outgas due to the mixing of the first polyarylene sulfide resin and the second polyarylene sulfide resin, the halogen of the existing polyarylene sulfide resin is additionally removed. It is possible to improve the heat resistance, flame resistance and/or durability of a molded article manufactured by using it.

The polyarylene sulfide mixed resin may have an oligomer content of 0.01 to 5% by weight based on the total weight of the polyarylene sulfide mixed resin, and specifically, it may be 0.05% by weight or more, 0.1% by weight or more, or 0.2% by weight or more, and , 3.00 wt% or less, 2.00 wt% or less, 1.50 wt% or less, 1.40 wt% or less, 1.39 wt% or less, 1.38 wt% or less, 1.37 wt% or less, 1.36 wt% or less, or 1.35 wt% or less. In the polyarylene sulfide resin, an additional polymerization reaction may occur due to mixing of the first polyarylene sulfide resin and the second polyarylene sulfide resin, so that the proportion of oligomers having a low molecular weight may be low. For this reason, defects occurring due to the oligomer during processing of the polyarylene sulfide mixed resin may be reduced, and processability may be improved.

The iodine content of the polyarylene sulfide mixed resin may be 0 to 10,000 ppm, specifically, 50 ppm or more, 100 ppm or more, 150 ppm or more, or 200 ppm or more, based on the total weight of the polyarylene sulfide mixed resin, and 7,000 ppm or less, 5,000 ppm or less, 5,000 ppm or less, 3,000 ppm or less, 2,000 ppm or less, 1,800 ppm or less, 1,600 ppm or less, or 1,500 ppm or less. The polyarylene sulfide mixed resin may have a low iodine content because the halogen of the existing polyarylene sulfide resin is additionally removed due to the mixing of the first polyarylene sulfide resin and the second polyarylene sulfide resin. The harm to the human body can be lowered.

In addition, the inorganic content of the polyarylene sulfide mixed resin may be 0 to 5,000 ppm, specifically, 1 ppm or more, 5 ppm or more, 10 ppm or more, or 50 ppm or more, 3,000 ppm or less, 1,000 ppm or less, 800 ppm or less, 639 ppm or less, 600 ppm or less, 500 ppm or less, or 400 ppm or less. The polyarylene sulfide mixed resin has an inorganic content adjusted to an appropriate range by diluting the second polyarylene sulfide resin having a high inorganic content due to the mixing of the first polyarylene sulfide resin and the second polyarylene sulfide resin, It can solve the problem of reducing the single yarn rate in textile applications and causing short circuits in electrical and electronic products.

[Post-processed polyarylene sulfide mixed resin]

According to an embodiment, a post-processed first polyarylene sulfide resin including a terminal group derived from a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound and a polymerization inhibitor are melt-polymerized and a compatibilizer; And a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound is mixed, and a post-processed polyarylene sulfide mixed resin 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 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 and the second polyarylene sulfide resin are as described above.

Post-processed polyarylene sulfide mixed resin

The post-processed polyarylene sulfide mixed resin may be a mixture of the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin. 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, the 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 the twin screw extruder becomes 0.02 to 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 phenol group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group.

In addition, the melting point, non-linearity index, branching index, and iodine content of the post-processed polyarylene sulfide mixed resin are the same as those described above for the post-processed first polyarylene sulfide resin, and the inorganic material of the post-processed polyarylene sulfide mixed resin The content is the same as described above for the polyarylene sulfide mixed resin.

Meanwhile, the weight average molecular weight of the post-processed polyarylene sulfide mixed resin may be 25,000 g/mol or more, 30,000 g/mol or more, 45,000 g/mol or more, or 47,000 g/mol or more, and 100,000 g/mol or less, 80,000 g/mol or more. mol or less, 75,000 g/mol or less, 70,000 g/mol or less, or 68,000 g/mol or less. 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, 19,000 g/mol or less, or 18,000 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, 70,000 g/mol or less, 65,000 g/mol or less, or 60,000 g/mol or less.

The melt viscosity of the post-processed polyarylene sulfide mixed resin is 1 Pa·s or more, 10 Pa·s or more, 50 Pa·s or more, 100 Pa·s or more, or 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, 1900 Pa s or more, or 2,000 Pa s or more, and may be 7,000 Pa s or less, 5,000 Pa s or less, 4,000 Pa s or less, or 3,000 Pa s or more It may be less than or equal to s.

The disulfide bond fraction of the post-processed polyarylene sulfide mixed resin may be 0 to 10.0 wt%, specifically, 0.01 wt% or more, 0.01 wt% or more, 0.1 wt% or more, or 0.2 wt% or more, and 10.0 wt% 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 may be below.

The amount of outgas of the post-processed polyarylene sulfide mixed resin may be 0.01 to 0.50 wt%, specifically, 0.01 wt% or more, 0.02 wt% or more, 0.03 wt% or more, or 0.04 wt% or more, and 0.30 wt% or less , 0.20 wt% or less, 0.18 wt% or less, 0.16 wt% or less, 0.15 wt% or less, 0.14 wt% or less, 0.13 wt% or less, 0.12 wt% or less, or 0.11 wt% or less.

The oligomer content of the post-processed polyarylene sulfide mixed resin may be 0.01 to 5 wt% based on the total weight of the post-processed polyarylene sulfide mixed resin, and specifically, 0.05 wt% or more, 0.1 wt% or more, or 0.2 wt% % or more, and may be 3.00 wt% or less, 2.00 wt% or less, 1.50 wt% or less, 1.25 wt% or less, 1.00 wt% or less, 0.90 wt% or less, 0.85 wt% or less, or 0.80 wt% or less.

The post-processed polyarylene sulfide mixed resin may exhibit an effect of having superior physical properties than the solution-polymerized polyarylene sulfide resin, while the amount of outgas is low at a level comparable to that of the melt-polymerized polyarylene sulfide resin.

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. It is possible to improve physical properties such as tensile strength and impact strength by improving compatibility at the same time.

[plastic surgery]

The above-described first polyarylene sulfide resin, post-processed first polyarylene sulfide resin, second polyarylene sulfide resin, polyarylene sulfide mixed resin, and post-processed polyarylene sulfide mixed resin may be prepared in various methods and forms without limitation. can be molded into Typically, the resin or the mixed resin 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.

[Production Example]

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. After 24 g of disulfide was added and the reaction was carried out for 1 hour, the reaction was further proceeded for 1 hour by gradually reducing the pressure to 0.5 torr or less, and then the reaction was terminated. processing to prepare PPS A1 as the first polyarylene sulfide resin.

Preparation A2: Preparation of PPS A2

About 1,500 g of PPS A2 as the first polyarylene sulfide resin was prepared in the same manner as in Preparation Example A1, except that 4.5 g of 2,2'-dithiodibenzoic acid was used instead of 24 g of diphenyldisulfide as a polymerization inhibitor. did.

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.

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 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer (2,2'-dithiodibenzoic acid) ( 4.5 g) was put into a twin-screw kneading extruder, and then 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 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, post-processed PPS C2 was prepared as a first polyarylene sulfide resin.

Preparation C3: Preparation of PPS C3

In the same manner as in Preparation C1, except that 0.3 parts by weight of bis(3-hydroxyphenyl) disulfide was used instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer, PPS C3 was prepared as a post-processed first polyarylene sulfide resin.

Preparation C4: Preparation of PPS C4

In the same manner as in Preparation C1, except that 0.3 parts by weight of bis(4-hydroxyphenyl) disulfide was used instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid as a compatibilizer, PPS C4 was prepared as a post-processed first polyarylene sulfide resin.

Preparation C5: Preparation of PPS C5

3-(triethoxysilyl)propane-1-thiol (3-(triethoxysilyl)propane-1-thiol) (Power chemical (made in China) SiSiB - PC2310) Except that 0.3 parts by weight was used, PPS C5 was prepared as a post-processed first polyarylene sulfide resin in the same manner as in Preparation Example C1.

Preparation C6: Preparation of PPS C6

As a compatibilizer, 0.3 parts by weight of (1,2-bis(3-(triethoxysilyl)propyl)disulfane (Power chemical 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.

Preparation C7: Preparation of PPS C7

As a compatibilizer, in the same manner as in Preparation C1, except that 0.3 parts by weight of 4-iodophenyl ethyl ether (Sigma-Aldrich Product No.: 538744) was used instead of 0.3 parts by weight of 2,2'-dithiodibenzoic acid, the post-processed preparation 1 PPS C7 was prepared as a polyarylene sulfide resin.

Polyarylene Sulfide Mixed Resin

Preparation D1 to D4: Preparation of PPS D1 to D4

The first polyarylene sulfide resin (PPS A1) prepared according to Preparation Example A1 and the second polyarylene sulfide resin (PPS B) prepared according to Preparation Example B were mixed in a twin-screw kneading extruder ( Bautek Twin Screw compounding extruder, L40/D19) was melt-mixed at 312°C and blended, and the blended resin was processed into pellets using a small strand cutter to prepare PPS D1 to D4 as polyarylene sulfide mixed resins.

Preparation D5: Preparation of PPS D5

The first polyarylene sulfide resin (PPS A1) prepared according to Preparation Example A1 and the second polyarylene sulfide resin (PPS B) prepared according to Preparation B were mixed in a twin-screw kneading extruder at the weight ratio shown in Table 1 below. It was mixed and blended at 25° C., and the blended resin was processed into pellets using a small strand cutter to prepare PPS D5 as a polyarylene sulfide mixed resin.

Post-processed polyarylene sulfide mixed resin

Preparation E1 to E9: Preparation of PPS E1 to E9

The weight ratio of the first polyarylene sulfide resin (PPS C1 to C7) prepared according to Preparation Examples C1 to C7 and the second polyarylene sulfide resin (PPS B) prepared according to Preparation Example B is shown in Table 2 below. It was melt-mixed and blended at 312° C. in a twin-screw kneading extruder, and the blended resin was processed into pellets using a small strand cutter to prepare PPS E1 to E9 as post-processed polyarylene sulfide mixed resins.

Preparation F1 and F2: Preparation of PPS F1 and F2

The post-processed first polyarylene sulfide resins (PPS C1 to C3) prepared according to Preparation Examples C1 to C3 were melt-mixed and blended at 312° C. in a twin-screw kneading extruder at the weight ratio shown in Table 2 below, and the blended resin was PPS F1 and F2 were prepared as a post-processed first polyarylene sulfide resin by processing into pellets using a small strand cutter.

[Experimental example]

The melting point, melting viscosity, non-linearity index, molecular weight, branching index, disulfide bond fraction, outgas amount and iodine content of the polyarylene sulfide resin prepared according to the preparation example were measured/derived by the following method, and the following Tables 3 to 5 shown in

(1) Melting point (Tm)

The melting point was heated at a rate of 10°C/min from 30°C to 320°C using a Q20 model differential scanning calorimeter (DSC) of TA instrument, cooled to 30°C, and then again at 30°C. It was measured while heating up to 320 degreeC at the rate of 10 degreeC/min.

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

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

The non-linearity index was calculated through Equation 2 below.

[Equation 2]

Nonlinearity index = 1 - (melt viscosity at a shear rate of ^{17.3 s -1} ) / (melt viscosity at a 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 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] = K×M ^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

The amount of outgas was quantified in weight % using a gas chromatograph (GC) mass spectrometer for the amount of gas generated by heating a sample of a predetermined amount of polyarylene sulfide resin or resin composition at 320° C. for 30 minutes.

(7) Iodine content

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

(8) oligomer content

Among the total peaks of the polyarylene sulfide resin shown in high temperature gel-permeation chromatography, the ratio of the polymer having a molecular weight of 1,000 g/mol or less was calculated as weight %, and the oligomer content was evaluated.

(9) mineral content

About 0.2 g of a polyarylene sulfide resin sample was heated and decomposed with a mixed acid (nitric acid/perchloric acid/sulfuric acid), diluted with ultrapure water, and the content of inorganic substances (Fe, Na, Ca, Li, etc.) was measured by ICP-AES (Agilent's 5100). model).

(10) compatibility

The polyarylene sulfide resin was measured through FT-IR (Agilent, Cary 670 model, measurement method: ATR-mode), and it was confirmed whether a functional group having compatibility with other resins was introduced into the main chain or side chain thereof.

Post-processed first polyarylene sulfide resin

As can be seen in the table above, PPS C1 to C7 in which the first polyarylene sulfide resin in which the diiodo aromatic compound, the first sulfur compound, and the polymerization inhibitor are melt-polymerized with a compatibilizer is post-processed with the compatibilizer, the first polyarylene sulfide resin is Compared to PPS A1 that is not post-processed as a compatibilizer, the amount of outgas, disulfide bond fraction, oligomer content and iodine content are significantly lower, as well as a high α value and a low nonlinearity index. could check

Moreover, PPS C1 has significantly lower disulfide bond fraction, oligomer content and iodine content than PPS A2 prepared by using the same compound as the compound used as a compatibilizer during post-processing in PPS C1 in the same amount as a polymerization inhibitor, It was confirmed that the α value was high and the nonlinearity index was low. In addition, functional groups compatible with other resins were not detected in PPS A2, whereas functional groups compatible with other resins were detected in PPS C1.

Polyarylene Sulfide Mixed Resin

As can be seen in the table above, PPS D1 to D5 in which the first polyarylene sulfide resin and the second polyarylene sulfide resin are blended, have a disulfide bond fraction and iodine content compared to PPS A1, which is the first polyarylene sulfide alone resin. was significantly lower, and the amount of outgas was significantly lower than that of PPS B, which is the second polyarylene sulfide-only resin, and it was confirmed that it was at a level corresponding to that of PPS A1. In addition, the oligomer content of PPS D1 to D5 was significantly lower than that of both PPS A1 and B.

On the other hand, PPS D1 to D4 in which the first polyarylene sulfide resin and the second polyarylene sulfide resin are melt-polymerized are compared to PPS D5 in which the first polyarylene sulfide resin and the second polyarylene sulfide resin are polymerized at room temperature. , it was confirmed that the disulfide bond fraction was significantly low.

Post-processed polyarylene sulfide mixed resin

As can be seen in the table above, PPS E1 to E9 in which the post-processed first polyarylene sulfide resin and the second polyarylene sulfide resin are blended are compared to the first polyarylene sulfide resins PPS A1, PPS F1 and F2. It was confirmed that the disulfide bond fraction and iodine content were significantly lower, and the inorganic content was significantly lower than that of PPS B, which is the second polyarylene sulfide-only resin. Moreover, PPS E1 to E9 have significantly lower outgas amount and oligomer content compared to all of PPS A1, F1, F2 and B, and have a functional group having compatibility with other resins unlike PPS A1, F1, F2 and B. was able to confirm

In addition, PPS E1 to E9 have significantly less disulfide bond fraction and amount of outgas compared to PPS D5 in which the first polyarylene sulfide resin and the second polyarylene sulfide resin that are not post-processed are blended, and, unlike PPS D5, other It was confirmed that it had a functional group having compatibility with the resin.

Claims (23)

a first polyarylene sulfide resin obtained by melt polymerization of a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor; and
A post-processed first polyarylene sulfide resin comprising end groups derived from a compatibilizer.
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 phenol group, an amino group, an amide group, a silane group, a sulfide group, and a sulfonate group, post-processed first polyarylene sulfide resin.
The method of claim 1,
The compatibilizer is a post-processed first polyarylene sulfide resin, which is a compound represented by one of the following Chemical Formulas 5 to 8:
[Formula 5]

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 having 1 or 2 carbon atoms or the substituted alkenyl group having 1 or 2 carbon atoms of ^{Z 1 '} to Z ^{4' has a substituent of an alkyl group or phenyl group having 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 6]

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 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 7]

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;
[Formula 8]

In the above formula,
Y ¹³ is selected from the group consisting of a halo group, -OB ²² , -SB ²³ , -COOB ²⁴ , NB ²⁵ B ²⁶ , -SO ₃ B ²⁷ and -NHCOB ²⁸ ,
B ²² to B ²⁸ are each independently selected from the group consisting of a hydrogen group, a sodium cation, a lithium cation, a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms, and a substituted or unsubstituted phenyl group,
W' is halogi;
Z ⁵ ' and Z ⁶ ' 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,
q is an integer from 1 to 3,
When Z ₅ ' and Z ₆ ' are an alkenyl group having 2 carbon atoms and are bonded to two adjacent carbon atoms, they may be connected to each other to form a benzene ring,
A substituted alkyl group or substituted phenyl group having 1 or 2 carbon atoms or a substituted phenyl group of ^{B 22} to B ^{28 has a substituent of an alkyl group or phenyl group having 1 or 2 carbon atoms,}
However, at least one of _{Y 13} is selected from the group consisting ^{of -OB 22} , -SB ²³ , -COOB ²⁴ , NB ²⁵ B ²⁶ , -SO ₃ B ²⁷ and -NHCOB ^{28 .}
The method of claim 1,
The post-processed first polyarylene sulfide resin, wherein the first polyarylene sulfide resin is post-processed using the compatibilizer at a temperature of 280 to 330°C.
The method of claim 1,
The post-processed first polyarylene sulfide resin, wherein the disulfide bond fraction of the post-processed first polyarylene sulfide resin is 0.001 to 1.5% by weight, or the amount of outgas is 0.001 to 0.10% by weight.
The method of claim 1,
The post-processed first polyarylene sulfide resin has a number average molecular weight of 7,500 to 20,000 g/mol, a weight average molecular weight of 30,000 to 80,000 g/mol, and a peak peak molecular weight of 15,000 to 50,000 g/mol. 1 polyarylene sulfide resin.
The method of claim 1,
Based on the total weight of the post-processed first polyarylene sulfide resin, the post-processed first polyarylene sulfide resin has an oligomer content of 0.01 to 1.38 wt%, or an iodine content of 100 to 7,000 ppm. 1 polyarylene sulfide resin.
a first polyarylene sulfide resin obtained by melt polymerization of a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor; and
A polyarylene sulfide mixed resin in which a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound is mixed.
9. The method of claim 8,
The first polyarylene sulfide resin and the second polyarylene sulfide resin are melt-mixed at 280 to 330°C, polyarylene sulfide mixed resin.
9. The method of claim 8,
A polyarylene sulfide mixed resin comprising 0.25 to 99 parts by weight of the second polyarylene sulfide resin based on 1 part by weight of the first polyarylene sulfide resin.
9. The method of claim 8,
A polyarylene sulfide mixed resin comprising 0.1 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.
9. The method of claim 8,
The polyarylene sulfide mixed resin has a disulfide bond fraction of 0.001 to 2.0 wt%, and an outgas amount of 0.001 to 0.20 wt% of the polyarylene sulfide mixed resin.
9. The method of claim 8,
Based on the total weight of the polyarylene sulfide mixed resin, the polyarylene sulfide mixed resin having an oligomer content of 0.01 to 1.38 wt% of the polyarylene sulfide mixed resin.
9. The method of claim 8,
Based on the total weight of the polyarylene sulfide mixed resin, the polyarylene sulfide mixed resin has an iodine content of 0 to 7,000 ppm, the polyarylene sulfide mixed resin.
a post-processed first polyarylene sulfide resin including end groups derived from a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound and a polymerization inhibitor are melt-polymerized and a compatibilizer; and
A post-processed polyarylene sulfide mixed resin in which a second polyarylene sulfide resin obtained by solution polymerization of a dihalo aromatic compound and a second sulfur compound is mixed.
16. The method of claim 15,
The post-processed polyarylene sulfide mixed resin, wherein the disulfide bond fraction of the polyarylene sulfide mixed resin is 0 to 2.0% by weight, and the amount of outgas is 0.001 to 0.20% by weight.
16. The method of claim 15,
The post-processed polyarylene sulfide mixed resin has a melt viscosity of 1,000 to 7,000 poise of the post-processed polyarylene sulfide mixed resin.
16. The method of claim 15,
The post-processed polyarylene sulfide mixed resin has a number average molecular weight of 9,000 to 20,000 g/mol, a weight average molecular weight of 30,000 to 80,000 g/mol, and a peak peak molecular weight of 20,000 to 75,000 g/mol, post-processed polyaryl Rensulfide blended resin.
16. The method of claim 15,
Based on the total weight of the post-processed polyarylene sulfide mixed resin, the post-processed polyarylene sulfide mixed resin has an iodine content of less than 5,000 ppm and an inorganic content of 0 to 600 ppm, post-processed polyarylene sulfide mixed resin profit.
16. The method of claim 15,
Based on the total weight of the post-processed polyarylene sulfide mixed resin, the post-processed polyarylene sulfide mixed resin has an oligomer content of 0.01 to 1.25 wt% of the post-processed polyarylene sulfide mixed resin.
preparing a first polyarylene sulfide resin in which a diiodo aromatic compound, a first sulfur compound, and a polymerization inhibitor are melt-polymerized; and
A method for producing a post-processed first polyarylene sulfide resin, comprising the step of post-processing the first polyarylene sulfide resin using a compatibilizer.
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
A method for producing a polyarylene sulfide mixed resin, comprising mixing the first polyarylene sulfide resin and the second polyarylene sulfide resin.
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 the first polyarylene sulfide resin and the second polyarylene sulfide resin; and
A method for producing a post-processed polyarylene sulfide mixed resin, comprising the step of post-processing the first polyarylene sulfide resin using a compatibilizer.