KR20140137534A - Brightness control and modifier agent for polyphenyl sulfide, method for preparing polyphenyl sulfide using thereof, and resin obtained by the method - Google Patents

Abstract

The present invention relates to a modified agent of polyphenylene sulfide resin for controlling brightness, a manufacturing method of a resin, and a polyphenylene sulfide resin using the same. More specifically, provided are a modified agent of polyphenylene sulfide resin for controlling brightness which turns the color of polyphenylene sulfide resin to bright brown from grey and reduces crystallization, a manufacturing method of a resin using the same, and polyphenylene sulfide resin using the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyphenylene sulfide resin, a modifier for controlling brightness of polyphenylene sulfide resin, a process for producing the same, and a polyphenylene sulfide resin, and a method for preparing polyphenyl sulfide,

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 existing 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 in pellet like existing polyester product, which avoids the problem of using fine powdered product. 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.

According to the present invention, there is provided a modifier for controlling the brightness of a polyphenylene sulfide resin, which is composed of at least one compound selected from monosulfide compounds and a disulfide compound.

According to the present invention, in the production of polyphenylene sulfide by melt-polymerizing a di-halogenated aromatic compound and an elemental sulfur, the above-described lightness-adjusting modifier is added to the dihalogenated aromatic compound in an amount of 0.001 To 0.02 moles per mole of the polyphenylene sulfide.

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, as described above, the modifier for controlling lightness can be added to the dihalogenated aromatic compound as a raw material of polyphenylene sulfide in an amount of 0.001 to 0.02 mol, more preferably 0.001 to 0.02 mol, per mol of the dihalogenated aromatic compound 0.011 mol.

Here, 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, specifically, 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, And the modifier for regulating the brightness of the resin is added in an amount of 0.1 to 2% based on the molar amount of the above-mentioned dihalogenated aromatic compound before the initiation of the polymerization reaction.

In this case, 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 to 1.45, To 1.35, where the elemental sulfur may be S8, S7, S6 or a mixture thereof, or S8, although not limited thereto.

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 this method has an L (brightness) in the Lab color coordinate 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 A light brown type polyphenylene sulfide resin can be obtained.

The polyphenylene sulfide resin actually obtained has a glass transition temperature of 70 to 120 캜, a crystallization temperature of 150 to 210 캜, 180 to 200 캜, or 190 to 200 캜, a melting temperature of 240 to 300 캜 , A viscosity of 700 to 500,000 P, and a number average molecular weight (Mn) of 20,000 to 120,000 g / mol.

The polyphenylene sulfide may be applied as a variety of molding materials such as films, sheets, fibers, injection molded articles, and LEDs.

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 53,744 poise and the number average molecular weight (Mn) was 73,358 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 27,723 poise and a number average molecular weight of 60,653 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 obtained 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 52,078 poise and a number average molecular weight of 72,697 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 18,889 poise and a number average molecular weight (Mn) of 54,322 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 3,217 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 obtained polyphenylene sulfide resin had a glass transition temperature of 106 占 폚, a crystallization temperature (Tc) of 176 占 폚, a melting temperature (Tm) of 271 占 폚, a viscosity of 113,750 poise and a number average molecular weight (Mn) of 90,991 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, and a disulfide-based compound. The modifier for controlling brightness of the polyphenylene sulfide resin is preferably at least one compound selected from the group consisting of a compound represented by formula
The method according to claim 1,
Wherein the monosulfide-based compound is represented by the following formula 1: < EMI ID =
[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.
The method according to claim 1,
Wherein the disulfide compound is represented by the following formula 2: < EMI ID =
(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.
The method according to claim 1,
Wherein at least one compound selected from the monosulfide compound and at least one compound selected from the disulfide compound is contained in a weight ratio of 1:99 to 99: 1.
The method according to claim 1,
Wherein the lightness-modifying-type modifier is a polymerization catalyst substitute for polyphenylene sulfide.
In the production of polyphenylene sulfide by melt polymerization of a di-halogenated aromatic compound and an elemental sulfur,
The method for producing polyphenylene sulfide as claimed in claim 1, wherein 0.001 to 0.02 moles of the modifier / regeneration modifier is added to the dihalogenated aromatic compound per mole of the halogenated aromatic compound prior to initiation of the polymerization reaction.
The method according to claim 6,
The above-mentioned 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 ≪ RTI ID = 0.0 > polyphenylene < / RTI > sulfide.
The method according to claim 6,
Wherein the molar ratio of the dihalogenated aromatic compound to the elemental sulfur is in the range of 0.6 to 1.45.
11. The method of claim 10,
Wherein the molar ratio of the dihalogenated aromatic compound to the elemental sulfur is in the range of 1 to 1.35.
10. The method according to claim 8 or 9,
Wherein said elemental sulfur is at least one selected from S8, S7 and S6.
The method according to claim 6,
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 >
A light brown series obtained by the method of claim 6 and having a L value (brightness) in the Lab color coordinates 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 , Polyphenylene sulfide resin.
13. The method of claim 12,
Wherein the polyphenylene sulfide resin has a crystallization parameter (delta) satisfying 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)).
13. The method of claim 12,
Wherein the polyphenylene sulfide resin has 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, 700 to 500,000 P, and a number average molecular weight (Mn) of 20,000 to 120,000 g / mol Polyphenylene sulfide resin.
13. The method of claim 12,
Wherein the polyphenylene sulfide resin is applied as a molding material selected from a film, a sheet, a fiber, an injection molded article, and an LED.