KR101679106B1 - Brightness control and modifier agent for polyphenyl sulfide, method for preparing polyphenyl sulfide using thereof, and resin obtained by the method - Google Patents
Brightness control and modifier agent for polyphenyl sulfide, method for preparing polyphenyl sulfide using thereof, and resin obtained by the method Download PDFInfo
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- KR101679106B1 KR101679106B1 KR1020130069453A KR20130069453A KR101679106B1 KR 101679106 B1 KR101679106 B1 KR 101679106B1 KR 1020130069453 A KR1020130069453 A KR 1020130069453A KR 20130069453 A KR20130069453 A KR 20130069453A KR 101679106 B1 KR101679106 B1 KR 101679106B1
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Abstract
The present invention relates to a modifier for controlling lightness of a polyphenylene sulfide resin, a method for producing a resin using the same, and a polyphenylene sulfide resin. More specifically, the present invention relates to a polyphenylene sulfide resin, And can lower the crystallinity, a process for producing a resin using the same, and a polyphenylene sulfide resin.
Description
The present invention relates to a modifier for controlling lightness of a polyphenylene sulfide resin, a method for producing a resin using the same, and a polyphenylene sulfide resin. More specifically, the present invention relates to a polyphenylene sulfide resin, And can lower the crystallinity, a process for producing a resin using the same, and a polyphenylene sulfide resin.
Polyphenylene sulfide (PPS) is a high-performance engineering thermoplastic that can be heated and shaped into a desired shape in a variety of manufacturing, sales and consumer applications. Polyphenylene sulfide can be used in the manufacture of fibers, films, coatings, injection molding compounds, and fiber-reinforced composites and is well suited for applications in the electrical, automotive and electrical / electronics industries. The polyphenylene sulfide may be incorporated alone or in combination with other materials, such as elastomeric materials, copolymers, resins, reinforcing agents, additives, other thermoplastic materials, and the like, as a manufacturing component.
The general molecular structure of these polyphenylene sulfides consists of alternating aromatic (phenylene) rings and sulfur atoms (in para-substituted patterns). The molecular structure provides polyphenylene sulfide which is a semi-crystalline polymer that can readily fill with a thermally stable crystalline lattice and has a high crystalline melting point below about 280 ° C and higher. Due to this molecular structure, polyphenylene sulfide is also more likely to burn during burning, making the material a unique flame retardant, as mentioned above. Moreover, such materials will typically not dissolve in the solvent at temperatures below about < RTI ID = 0.0 > 200 C. < / RTI >
Polyphenylene sulfide polymers, including semi-crystalline polyphenylene sulfide, are attractive engineering plastics because they provide a combination of excellent properties. For example, polyphenylene sulfide provides resistance to aggressive chemical environments and also provides precise molding for tight tolerances.
Moreover, polyphenylene sulfide is thermally stable, nonflammable without inherent flame retardant additives, and has excellent dielectric / insulation properties. Other properties include dimensional stability, high modulus, and creep resistance. The advantageous properties of polyphenylene sulfide are due in part to the stable chemical bonding of the molecular structure which gives a relatively high degree of molecular stability for both pyrolysis and chemical reactivity .
The polyphenylene sulfide resins proposed in US Pat. Nos. 4,746,758 and 4,786,713 can be prepared by using diiodo compounds instead of dichloro compounds and metal sulfides in the conventional process, This method corresponds to a method of producing a resin by using solid sulfur and heating directly without a polar solvent.
This method consists of two steps of iodination and polymerization. In the iodination process, aryl compounds are reacted with iodine to obtain diiodide compounds. In the polymerization process, these are reacted with solid sulfur to form high molecular weight PAS . During the reaction, iodine is generated in the form of vapor, which can be recovered and reacted with the aryl compound, so that iodine is substantially a catalyst.
According to these methods, since the byproduct is iodine, there is no problem of increasing the electric conductivity and it can be recovered easily from the reactant, so that the content to be contained in the final product can be lowered more easily than the metal salt content of the conventional process, and the recovered iodine It is possible to reduce the amount of waste. Secondly, since no solvent is used in the polymerization process, the product can be made into pellets like existing polyester products, which avoids the problem of using fine powdered products. Finally, since the molecular weight of the final PAS can be increased much more than the conventional process, there is no need to go through a post-treatment process which is disadvantageous to physical properties.
However, the problem to be solved in this new process is that the lightness of the resin is dark gray, so that it must contain a separate additive that increases the lightness close to the white color.
Therefore, it is necessary to develop a process capable of effectively producing polyphenylene sulfide having high heat resistance, chemical resistance, mechanical strength and high brightness of the resin in the process.
Accordingly, the present inventors have completed the present invention while continuing the study on a modifier for controlling brightness of a polyphenylene sulfide resin capable of brightening the lightness of a polyphenylene sulfide resin to be produced.
That is, an object of the present invention is to provide a modifier for controlling lightness of a polyphenylene sulfide resin capable of discoloring the color of a polyphenylene sulfide resin to be produced from gray to light brown and lowering crystallinity, Phenylene sulfide resin.
According to the present invention,
And at least one compound selected from a disulfide compound and a monosulfide compound, and a modifier compound capable of regulating brightness of the polyphenylene sulfide resin.
Further, according to the present invention, in the production of polyphenylene sulfide by melt-polymerizing a dihalogenated aromatic compound and an elemental sulfur,
Wherein the above-mentioned lightness-adjusting modifier is added in an amount of 0.1 to 2 mol% based on 100 mol% of the above-mentioned dihalogenated aromatic compound before initiation of the polymerization reaction.
Further, according to the present invention, it is possible to obtain L (brightness) of 42.6 to 84.7, a value (red to green) of -1.2 to 13.3 and a b value (yellow to blue) of 36.2 to 61.2 Based light-brown polyphenylene sulfide resin.
Further, according to the present invention, there is provided a polyphenylene sulfide resin, which is obtained by the above-described method, wherein the crystallization parameter? Satisfies the following equation.
[Equation 1]
20?? N -? M? 30
ΔM is the crystallization temperature (Tc, ° C) of the polyphenylene sulfide resin obtained when the modifier of claim 1 is not added, and δM is the crystallization temperature (Tc, ° C) of the polyphenylene sulfide resin obtained when the modifier of claim 1 is added. , ° C)).
Hereinafter, the present invention will be described in more detail.
The present invention has technical features to provide a modifier for controlling the brightness of a polyphenylene sulfide resin, which is composed of at least one compound selected from a monosulfide compound and at least one compound selected from a disulfide compound.
The monosulfide compound is characterized by being represented by the following formula (1).
[Chemical Formula 1]
Wherein R1 and R1 'are independently selected from hydrogen, halogen or alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms.
Further, the disulfide compound is characterized by being represented by the following formula 2.
(2)
Wherein R2 and R2 'are independently selected from hydrogen, halogen or alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms.
Specifically, the light modifier / modifier is used in an amount of 0.1 to 2 mol%, or 0.1 to 2 mol%, based on 100 mol% of the dihalogenated aromatic compound, relative to the dihalogenated aromatic compound as a raw material of polyphenylene sulfide, To 1 mol%.
In this case, the sulfide compound represented by Formula 1 and the disulfide compound represented by Formula 2 may be contained in a weight ratio of 1:99 to 99: 1, or 30:70 to 70:30.
In particular, the light modifying and conditioning modifier according to the present invention is characterized by being used as a polymerization catalyst substitute for polyphenylene sulfide.
In addition, in the case of applying the modifier for improving brightness control of the present invention, it is possible to identify the improvement of brightness by discoloring the resin color which is gray when the modifier is combined with lightness modifier.
Specifically, a method for producing polyphenylene sulfide by using such a lightness-modifying modifier is as follows. In the production of polyphenylene sulfide by melt polymerization of a dihalogenated aromatic compound and an elemental sulfur, The modifier for regulating the brightness of the resin is added in an amount of 0.1 to 2 mol% based on 100 mol% of the above-mentioned dihalogenated aromatic compound, And the like.
Wherein the dihalogenated aromatic compound is an aromatic compound such as benzene which is para-substituted with at least one halogen selected from bromine, iodine and chlorine, the molar ratio of the dihalogenated aromatic compound to the elemental sulfur is 0.6: 1 to 1.45: 1, Or within the range of 1: 1 to 1.35: 1, where the elemental sulfur may be S8, S7, S6 or a mixture thereof, or S8.
In the present invention, the melt polymerization is carried out by using a shell-and-tube reactor at a temperature of 200 to 250 ° C. and a reduced pressure of 200 to 100 torr at a temperature of 260 to 320 ° C. and 50 to 0 or 30 to 0 torr Till Can be performed. For example, the reaction pressure can be either solution or melt-polymerized while being applied to a pressure of less than 200 torr to a pressure of less than 0 torr, and the production method can be batch, semi-batch, continuous process.
Particularly, in the present invention, a polyphenylene sulfide resin having a high brightness of a resin can be obtained without containing a conventionally used catalyst such as 1,4-dihalogen-2-nitrobenzene and 1,3-dihalogen-2-nitrobenzene The effective preparation is illustrated by the following examples.
The polyphenylene sulfide resin obtained by such a method has an L (brightness) in the Lab color coordinate of 35 to 90 or 42.6 to 84.7, a value (red to green) of -5 to 13.3 or -1.2 to 13.3, a light brown series polyphenylene sulfide resin having a yellow to blue of 30 to 65 or 36.2 to 61.2 can be obtained.
The polyphenylene sulfide resin actually obtained has a glass transition temperature of 70 to 120 캜, 100 to 110 캜 or 105 to 110 캜, a crystallization temperature of 150 to 210 캜, or 170 to 200 캜, or A melt temperature of 240 to 300 占 폚, 260 to 290 占 폚 or 275 to 277 占 폚, a viscosity of 700 to 300000 P (poise), 10000 to 10000 P or 25000 to 55000 P, a number average molecular weight (Mn) 120,000 g / mol, 50,000 to 100,000 g / mol or 60,000 to 75,000 g / mol.
The polyphenylene sulfide can be applied as various molding materials such as films, sheets, fibers, injection molded articles, fiber reinforced composites, and the like.
As described above, according to the present invention, a modifier for controlling lightness of a polyphenylene sulfide resin capable of changing the hue of polyphenylene sulfide resin from gray to light brown and lowering crystallinity, And a polyphenylene sulfide resin.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
Example One
2L, titanium-coated stainless steel shell-and-tube reactor was charged with 721.5 g of para-iodobenzene, 56 g of sulfuric acid sulfur (S8), 1.02 g of a sulfide compound in which R1 and R1 ' , And R2 'is H, and the reaction temperature and pressure were polymerized at 230 ° C. under a pressure of 200 torr to 320 ° C. under 0 torr to prepare a polyphenylene sulfide resin.
The glass transition temperature, crystallization temperature (Tc) and melting temperature (Tm) of the prepared polyphenylene sulfide resin were measured using a Differential Scanning Calorimeter (DSC) manufactured by TA Instrument. As a result, the glass transition temperature was 108 占 폚, the crystallization temperature (Tc) was 175 占 폚, and the melting temperature (Tm) was 275 占 폚.
Further, the melt viscosity was measured using ARES manufactured by TA Instrument, and the number average molecular weight (Mn) was obtained in terms of the following formula.
log (n) = 1.473 + 0.2873 * log (?)
(n: polymerization degree,?: melt viscosity (poise)).
As a result, the viscosity was 53744 poise and the number average molecular weight (Mn) was 73358 g / mol.
Further, L * (brightness), a * (Red to Gree), and b * (Yellow to Blue) were measured as color by using a color meter of X-Rite (Color-Eye 7000A).
As a result, L * was 84.7, a * was -1.2, and b * was 36.2.
Example 2
In the same manner as in Example 1 except that 1.225 g of the sulfide compound represented by the general formula (1) in which R1 and R1 'are H, and 0.955 g of the disulfide compound in which R2 and R2' .
The obtained polyphenylene sulfide resin had a glass transition temperature of 108 ° C, a crystallization temperature (Tc) of 193 ° C, a melting temperature (Tm) of 276 ° C, a viscosity of 27723 poise and a number average molecular weight of 60653 g / mol . L * was 42.6, a * was 13.3, and b * was 50.8.
Example 3
In the same manner as in Example 1 except that 1.63 g of the sulfide compound represented by the general formula (1) in which R1 and R1 'are H, and 0.4775 g of the disulfide compound in which R2 and R2' .
The resulting polyphenylene sulfide resin had a glass transition temperature of 108 占 폚, a crystallization temperature (Tc) of 185 占 폚, a melting temperature (Tm) of 277 占 폚, a viscosity of 52078 poise and a number average molecular weight of 72697 g / mol . L * was 82.3, a * was 2.4, and b * was 61.2.
Comparative Example One
Example 1 was repeated except that the sulfide compound in which R1 and R1 'in Formula 1 were H and the disulfide compound in which R2 and R2' in Formula 2 were H was 2.4875 g. The same process was repeated.
The obtained polyphenylene sulfide resin had a glass transition temperature of 104 占 폚, a crystallization temperature (Tc) of 207 占 폚, a melting temperature (Tm) of 276 占 폚, a viscosity of 18889 poise and a number average molecular weight (Mn) of 54322 g / mol. L * was 23.2, a * was 13.4, and b * was 35.1.
Comparative Example 2
In Example 1, the same procedure as in Example 1 was carried out except that 2.0375 g of a sulfide compound in which R 1 and R 1 'in Formula 1 were H, and a disulfide compound in which R 2 and R 2' And repeated.
The glass transition temperature of the prepared polyphenylene sulfide resin was 107 占 폚, the crystallization temperature (Tc) was 200 占 폚, the melting temperature (Tm) was 278 占 폚, the viscosity was 3217 poise and the number average molecular weight (Mn) g / mol. L * was 25.1, a * was 15.2, and b * was 37.5.
Comparative Example 3
In Example 1, the same processes as in Example 1 were repeated except that the compounds of Formulas 1 and 2 were not introduced and 3.05 g of 1,4-diiodo-2-nitrobenzene was added.
The glass transition temperature of the prepared polyphenylene sulfide resin was 106 占 폚, the crystallization temperature (Tc) was 176 占 폚, the melting temperature (Tm) was 271 占 폚, the viscosity was 113750 poise and the number average molecular weight (Mn) g / mol. L * was 31.1, a * was -28.4, and b * was 26.6.
From the above results, it can be understood from the results of Examples 1 to 3 that the sulfide-based compound of Formula 1 and the disulfide-based compound of Formula 2 were added prior to the initiation of polymerization in the preparation of the polyphenylene sulfide resin, And it was confirmed that the crystallization temperature can be reduced to 20 to 30 占 폚.
On the other hand, in Comparative Examples 1 to 3, in which no one component was added, such brightness improvement effect and crystallization temperature reduction effect could not be confirmed.
Claims (15)
A monosulfide-based compound represented by the following formula 1 and a disulfide-based compound represented by the following formula 2 in a weight ratio of 1:99 to 99: 1 are used as a catalyst, with 100 mol% or more of the dihalogenated aromatic compound, 0.1 to 2 mol% as a reference,
Wherein the molar ratio of the dihalogenated aromatic compound to the elemental sulfur is in the range of 1: 1 to 1.35: 1,
Wherein the di-halogenated aromatic compound is an aromatic compound para-substituted with at least one halogen selected from bromine, iodine and chlorine.
[Chemical Formula 1]
(2)
Wherein R 1 , R 1 ', R 2 and R 2 ' are independently selected from hydrogen, halogen or alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms.
Wherein said elemental sulfur is at least one selected from S8, S7 and S6.
Wherein the molten polymerisation is carried out at a temperature of 200 to 250 DEG C and a reduced pressure of 200 to 100 torr at a temperature of 260 to 320 DEG C and 50 to 0 torr using a shell and tube reactor, ≪ / RTI >
Wherein the polyphenylene sulfide resin has a crystallization parameter (delta) satisfying the following equation.
[Equation 1]
20?? N -? M? 30
ΔN is the crystallization temperature (Tc, ° C.) of the polyphenylene sulfide resin obtained when the lightness-modifying additive according to claim 6 is not used, and δM is the polyphenylene sulfide obtained when the lightness-modifying modifier of claim 6 is added The crystallization temperature (Tc, 占 폚) of the resin)
The polyphenylene sulfide resin is characterized by having a glass transition temperature of 70 to 120 캜, a crystallization temperature of 150 to 210 캜, a melting temperature of 240 to 300 캜, a viscosity of 700 to 300000 P and a number average molecular weight (Mn) of 20,000 to 120,000 g / mol Polyphenylene sulfide resin.
Wherein the polyphenylene sulfide resin is applied as a molding material selected from the group consisting of a film, a sheet, a fiber, an injection molded product (excluding film, sheet, and fiber), and a fiber reinforced composite material.
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| JPH06256655A (en) * | 1993-03-09 | 1994-09-13 | Kureha Chem Ind Co Ltd | Polyphenylene sulfide composition having color tone stability |
| WO2008082265A1 (en) * | 2007-01-04 | 2008-07-10 | Sk Chemicals Co., Ltd. | Polyarylene sulfide resin with excellent luminosity and preparation method thereof |
| KR101174073B1 (en) * | 2007-01-05 | 2012-08-16 | 에스케이케미칼주식회사 | Method for production of polyarylene sulfide resin with excellent luminosity and the polyarylene sulfide resin |
| KR20130025016A (en) * | 2011-09-01 | 2013-03-11 | 주식회사 엘지화학 | A method for preparing polyarylene sulfides |
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