KR20180097002A - Sulfur containing polymer and method for preparing sulfur containing polymer - Google Patents

Abstract

The present invention provides a sulfur-containing polymer and a method for preparing the sulfur-containing polymer, wherein the sulfur-containing polymer has high thermal stability and low fragility, thereby having excellent post-processing properties while maintaining excellent optical characteristics. The sulfur-containing polymer comprises a sulfur element; a first aromatic compound having one vinyl group; and a second aromatic compound having two vinyl groups as a constituent unit. The glass transition temperature of the sulfur-containing polymer is 70°C or higher.

Description

TECHNICAL FIELD [0001] The present invention relates to a sulfur-containing polymer and a sulfur-containing polymer,

The present invention relates to a polymer containing sulfur in a chemical structure and a method for producing the polymer.

Sulfur - containing macromolecules have been actively studied as functional polymers in recent years. However, since sulfur which can be obtained as a by-product in the desulfurization process of crude oil is weak in brittleness and large in crystallinity, utilization of sulfur other than that used for producing sulfuric acid or vulcanization of rubber is not high. Particularly, when inserting sulfur into the macromolecules, there are problems such as reactivity and difficulty in synthesis of a soluble monomer, and there is a problem that a considerably complicated step is required to obtain a target macromolecule. Nevertheless, in the case of macromolecules containing sulfur, their refractive index is high, and they are widely seen as potential materials in the field of optics, and various studies and attempts have been made.

An embodiment of the present invention provides a sulfur-containing polymer having excellent optical properties, high infrared transmittance, high thermal stability, low brittleness and excellent processability.

Another embodiment of the present invention provides a unique method for preparing the sulfur-containing polymer.

In one embodiment of the invention, a sulfur element; A first aromatic compound having one vinyl group; And a second aromatic compound having two vinyl groups as structural units and having a glass transition temperature (Tg) of 60 캜 or higher.

In another embodiment of the present invention, there is provided a process for the preparation of (a) a sulfur containing feedstock, a first aromatic compound having one vinyl group; And a second aromatic compound having two vinyl groups while heating to prepare a mixture; (b) stirring the mixture while heating; And (c) annealing the mixture. The present invention also provides a method for producing a sulfur-containing polymer.

The sulfur-containing polymer has an improved mechanical property and has an advantage of high thermal stability, low embrittlement, and excellent post-processability while maintaining excellent optical characteristics.

In addition, the process for preparing the sulfur-containing polymer provides a unique method for producing the sulfur-containing polymer having such advantages.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which: These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art to which the invention pertains. Only.

In one embodiment of the invention, a sulfur element; A first aromatic compound having one vinyl group; And a second aromatic compound having two vinyl groups as constitutional units and having a glass transition temperature (Tg) of about 60 ° C or higher.

The sulfur-containing polymer may have a glass transition temperature (Tg) of at least about 60 ° C, for example, about 60 ° C to about 75 ° C, for example, from about 60 ° C to about 75 ° C, About 60 < 0 > C to about 70 < 0 > C. The glass transition temperature (Tg) of the sulfur-containing polymer can be derived from a rheometer analysis. When the glass transition temperature (Tg) of the sulfur-containing polymer satisfies the above range, the thermal stability, workability, and moldability can be improved as compared with the case where the glass transition temperature (Tg) is conventionally about 0 to 15 deg.

Specifically, the sulfur-containing polymer includes a sulfur element as a constituent unit, a first aromatic compound having one vinyl group, and a second aromatic compound having two vinyl groups.

The sulfur element means atomic sulfur and is derived from a sulfur compound of the S ₈ structure in which 8 sulfur atoms form a covalent bond. Thus, the sulfur element is present in the chemical structure of the sulfur-containing polymer as a covalent bond in the form of - [S] _n - (n is an integer of 1 to 8).

The sulfur compound of the S ₈ structure is the most thermodynamically stable, and has a low solubility in an organic solvent which is commonly used, and is not utilized other than the production of sulfuric acid or vulcanization of rubber. Nevertheless, the sulfur-containing polymer according to one embodiment of the present invention can be produced by processing a sulfur compound of the S ₈ structure together with the first aromatic compound and the second aromatic compound through a predetermined process , A sulfur element derived from the sulfur compound of the above S ₈ structure can be contained as a constitutional unit. As a result, the sulfur-containing polymer can be easily controlled in optical properties such as refractive index by controlling its sulfur content.

The sulfur-containing polymer may comprise from about 40% to about 70% by weight of the sulfur element, for example, from about 40% to about 60% by weight, for example, from about 45% About 55% by weight. If the content of the sulfur element is too small, the brittleness is weak and it may be easily crumbled. If the content of the sulfur element is too large, depolymerization may occur.

The first aromatic compound and the second aromatic compound all have a vinyl group. At this time, the vinyl group performs a radical reaction with the sulfur compound of the S ₈ structure, and as a result, exists as a carbon-sulfur single bond in the sulfur-containing polymer.

By using an aromatic compound having a benzene structure as the compound having a vinyl group in this way, it can be advantageous in securing a refractive index, infrared transmittance and thermal stability as compared with the case of using a linear or branched aliphatic compound.

Further, by mixing the first aromatic compound having one vinyl group and the second aromatic compound having two vinyl groups, the brittleness is lowered and the modulus and workability are maintained at a desired level May be advantageous to the following.

The weight ratio of the first aromatic compound to the second aromatic compound can be from about 10:60 to about 30:20, and can be, for example, from about 10:30 to about 10:10. When the weight ratio of the first aromatic compound and the second aromatic compound is out of the range, the first aromatic compound and sulfur; Or the second aromatic compound and the sulfur are bonded to each other, and the sulfur is not uniformly dispersed in the chemical structure of the sulfur-containing polymer, and a domain may be formed.

Specifically, the first aromatic compound may include at least one compound represented by the following general formula (1).

[Chemical Formula 1]

Wherein R is independently an alkyl group having 1 to 10 carbon atoms, an amino group, an alkylamino group having 1 to 10 carbon atoms, a halogen group or an alkylhalogen group having 1 to 10 carbon atoms, and n is an integer of 0 to 5.

The second aromatic compound may be at least one selected from the group consisting of 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, . ≪ / RTI >

By using the above-mentioned compounds as the first aromatic compound and the second aromatic compound, excellent thermal stability and processability can be realized by forming the constituent unit of the polymer together with the sulfur element.

The sulfur-containing polymer may have a refractive index of from about 1.650 to about 1.870, for example, from about 1.700 to about 1.750. The refractive index of the sulfur-containing polymer can be measured using a prism coupler after curing in an oven at 80 to 130 ° C for 24 to 60 hours.

In addition, the sulfur-containing polymer may have a transmittance of about 40% to about 90%, for example, about 60% to about 80%, for infrared (mid-IR) of 3 탆 to 5 탆 wavelength. The infrared transmittance of the sulfur-containing polymer can be measured by infrared spectroscopy after curing in an 80 ° C to 130 ° C oven for 24 to 60 hours.

In addition, the modulus of the sulfur-containing polymer can be from about 1.2 GPa to about 1.8 GPa, and can be, for example, from about 1.4 GPa to about 1.6 GPa. The modulus of the sulfur-containing polymer can be measured using a universal material tester (UTM) after curing in an 80 ° C to 130 ° C oven for 24 to 60 hours.

Both the refractive index, the infrared (mid-IR) transmittance and the modulus of the sulfur-containing polymer satisfy the respective ranges described above, so that the sulfur-containing polymer can attain excellent optical properties, thermal stability and workability, Optical fields, military fields, medical fields, and the like.

In another embodiment of the present invention, there is provided a process for the preparation of (a) a sulfur containing feedstock, a first aromatic compound having one vinyl group; And a second aromatic compound having two vinyl groups while heating to prepare a mixture; (b) stirring the mixture while heating; And (c) annealing the mixture. The present invention also provides a method for producing a sulfur-containing polymer.

Through the process for producing the sulfur-containing polymer, it is possible to produce the sulfur-containing polymer as described above. That is, the sulfur-containing polymer prepared through the above-described method is a sulfur element; A first aromatic compound having one vinyl group; And a second aromatic compound having two vinyl groups as constitutional units, and may have a glass transition temperature (Tg) of 60 DEG C or higher.

The sulfur-containing polymer may have a glass transition temperature (Tg) of about 60 캜 or higher, for example, about 60 캜 to about 75 캜, such as about 60 캜 to about 70 캜. The matters relating to the first aromatic compound and the second aromatic compound are as described above.

In the method for producing the sulfur-containing polymer, the sulfur feedstock may be a sulfur compound of the S ₈ structure. As described above, the sulfur compound of the S ₈ structure is the most thermodynamically stable, and has a low solubility in an organic solvent that is commonly used, and is less useful than vulcanization of sulfuric acid or vulcanization of rubber. Nevertheless, in the method of preparing the sulfur-containing polymer according to an embodiment of the present invention, the sulfur compound of the S ₈ structure is heated while being mixed with the first aromatic compound and the second aromatic compound, ) And (c), the sulfur-containing polymer can be used as the sulfur-containing feedstock for producing the sulfur-containing polymer. Thus, the sulfur content of the sulfur-containing polymer produced through the above-mentioned method for producing a sulfur-containing polymer can be controlled to easily control optical characteristics such as refractive index.

In step (a), the components are mixed while heating. Specifically, the step (a) may be performed at about 110 ° C to about 200 ° C, and may be performed at, for example, about 120 ° C to about 150 ° C . By performing at such a temperature, the sulfur feedstock can be melted into a reaction-active state, and can be uniformly mixed with the first aromatic compound and the second aromatic compound.

At this time, the step (a) may include a1) first mixing the sulfur feedstock and the first aromatic compound, and (a2) second mixing the second aromatic compound. The components can be more uniformly mixed by preferentially mixing the sulfur feedstock and the first aromatic compound and subsequently mixing the second aromatic compound and the reactivity between the first aromatic compound and the sulfur, By the difference in reactivity between the second aromatic compound and sulfur, a sulfur polymer having a uniform fraction can be obtained.

In the mixture prepared in step (a), the content of the sulfur-containing feedstock may be from about 40% by weight to about 70% by weight, from about 40% by weight to about 60% by weight, By weight to about 55% by weight. If the content of the sulfur element is too small, the brittleness is weak and it may be easily crumbled. If the content of the sulfur element is too large, depolymerization may occur.

Also, the weight ratio of the first aromatic compound to the second aromatic compound in the mixture may be from about 10:60 to about 30:20, and may be, for example, from about 10:30 to about 10:10.

When the weight ratio of the first aromatic compound and the second aromatic compound is out of the range, the first aromatic compound and sulfur; Or the second aromatic compound and the sulfur are bonded to each other, and the sulfur is not uniformly dispersed in the chemical structure of the sulfur-containing polymer, and a domain may be formed.

In the above-mentioned method for producing a sulfur-containing polymer, the step (b) is a step of stirring while heating a mixture in which the respective components are mixed, wherein the sulfur feedstock, the first aromatic compound and the second aromatic compound are chemically And then converted into a sulfur-containing polymer.

The step (b) may be performed at a temperature of about 110 ° C to about 200 ° C, for example, at a temperature of about 120 ° C to about 150 ° C. In addition, the stirring speed can be from about 200 rpm to about 500 rpm, for example from about 300 rpm to about 400 rpm.

The step (b) may be carried out under the conditions of the temperature and the stirring speed so that the molten sulfur feedstock and the first aromatic compound and the second aromatic compound in the step (a) , And can be manufactured in a state easy to handle in the subsequent step (c).

Also, in the step (b), the mixture may be stirred until its viscosity reaches about 1,000,000 cps to about 20,000,000 cps. The viscosity of the mixture means the viscosity at the performance temperature of step (b). When the viscosity of the mixture falls within the above range, the sulfur, the first aromatic compound and the second aromatic compound are reacted so as to have a desired cross-link density, and through the subsequent step (c) And it may be advantageous to realize advantages of low brittleness.

In the method for producing a sulfur-containing polymer, the step (c) is a step of annealing the gel-like mixture through the step (b). The step (c) is a separate step distinguishing the step (b) from the step (b), wherein the step (b) is a step of post-treating the mixture prepared to have an appropriate crosslink density through a crosslinking reaction.

Specifically, the step (c) may be a step of placing the mixture at about 90 ° C to about 130 ° C for about 24 hours to about 60 hours, followed by cooling at room temperature. By annealing the mixture under such warm and time conditions, a sulfur-containing polymer having a high glass transition temperature (Tg) as described above and having excellent thermal stability and post-processability can be produced.

As described above, the sulfur-containing polymer produced by the above-mentioned method for producing a sulfur-containing polymer can satisfy both the refractive index, the mid-IR transmittance and the modulus in a predetermined range. As a result, And medical fields. The refractive index, the infrared (mid-IR) transmittance and the angular range of the modulus are as described above for the sulfur-containing polymer.

In addition, the sulfur-containing polymer prepared through the above-mentioned method for producing a sulfur-containing polymer is excellent in post-processability and can be used particularly in the production of an infrared (mid-IR) transmission lens.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

< Example  And Comparative Example >

Example  One

The mixture was prepared by mixing a sulfur compound having an S ₈ structure and styrene at 120 ° C and then mixing 1,3-divinylbenzene at the same temperature. The mixture was stirred at a temperature of 120 ° C at a stirring speed of 350 rpm and stirred until the gel had a viscosity of 15,000,000 cps at the same temperature. The gel-like mixture was placed at a temperature of 110 ° C for 48 hours and then cooled at room temperature to prepare a sulfur-containing polymer. The sulfur compound of the S ₈ structure in the mixture was 50% by weight, and the weight ratio of styrene to 1,3-divinylbenzene was 1: 3.

Example  2

The mixture was prepared by mixing a sulfur compound having an S ₈ structure and styrene at 120 ° C and then mixing 1,3-divinylbenzene at the same temperature. The mixture was stirred at a temperature of 120 ° C at a stirring speed of 350 rpm and stirred until the gel had a viscosity of 15,000,000 cps at the same temperature. The gel-like mixture was placed at a temperature of 110 ° C for 48 hours and then cooled at room temperature to prepare a sulfur-containing polymer. The sulfur compound of the S ₈ structure in the mixture was 50 wt%, and the weight ratio of styrene to 1,3-divinylbenzene was 1: 1.

Comparative Example  One

A mixture was prepared by mixing a sulfur compound having an S ₈ structure with 1,4-diisopropenylbenzene at 180 ° C. The mixture was stirred at a temperature of 180 ° C at a stirring speed of 350 rpm and stirred until the viscosity of the gel reached 15,000,000 cps at the same temperature. The gel-like mixture was placed at a temperature of 110 ° C for 48 hours and then cooled at room temperature to prepare a sulfur-containing polymer. The sulfur compound of the S ₈ structure in the mixture was 50% by weight.

Comparative Example  2

A mixture was prepared by mixing a sulfur compound of the S ₈ structure with styrene at 120 ° C. The mixture was stirred at a temperature of 120 ° C at a stirring speed of 350 rpm and stirred until the viscosity of the gel reached 1,000 cps at the same temperature. The gel-like mixture was placed at a temperature of 110 ° C for 48 hours and then cooled at room temperature to prepare a sulfur-containing polymer. The sulfur compound of the S ₈ structure in the mixture was 50% by weight.

Comparative Example  3

The procedure of Example 1 was repeated except that the gel-like mixture was not placed at a temperature of 110 ° C for 48 hours and was immediately cooled at room temperature to prepare a sulfur-containing polymer. Respectively.

Comparative Example  4

The procedure of Example 2 was repeated except that the gel-like mixture was not placed at a temperature of 110 ° C for 48 hours and was immediately cooled at room temperature to prepare a sulfur-containing polymer. Respectively.

Comparative Example  5

In the same manner as in Comparative Example 1, except that the gel-type mixture was not placed at a temperature of 110 ° C. for 48 hours and was immediately cooled at room temperature to prepare a sulfur-containing polymer, Respectively.

<Evaluation>

Experimental Example  1: Glass transition temperature ( Tg )

The glass transition temperature (Tg) of each of the sulfur-containing polymers of the Examples and Comparative Examples was measured using a rheometer. The results are shown in Table 1 below.

Glass Transition Temperature [캜] Remarks Example 1 74.4 Example 2 60.8 Comparative Example 1 6.0 Comparative Example 2 Not measurable The measurement range of the instrument is out of range. Comparative Example 3 13.5 Compare to 4 18.3 Comparative Example 5 6.6

Experimental Example  2: Evaluation of optical characteristics

The sulfur-containing polymers of each of the above Examples and Comparative Examples were cured in an oven at 120 ° C for 48 hours and then refractive index was measured using a prism coupler apparatus (SAIRON, SPA4000). In addition, a specimen having a thickness of 0.1 to 0.15 mm was manufactured using a Fourier transform infrared spectrometer (Perkin Elmer, Frontier ^TM ), and the infrared (mid-IR) transmittance of 5 탆 was measured. The results are shown in Table 2 Same as.

Refractive index Infrared Transmittance [%] Remarks Example 1 1.754 75 Example 2 1.747 70 Comparative Example 1 1.761 70 Comparative Example 2 - - No specimen production (liquid) Comparative Example 3 1.742 72 Comparative Example 4 1.732 68 Comparative Example 5 1.735 70

Experimental Example  3: Modulous  evaluation

The sulfur-containing polymers of each of the examples and comparative examples were cured in an oven at 120 캜 for 48 hours and then evaluated for tensile strength at room temperature using a universal material tester apparatus (Zwick roell, Z100) (ASTM D638 ). The results are shown in Table 3 below. &Lt; tb &gt; &lt; TABLE &gt;

Modulus [GPa] Remarks Example 1 1.5 Example 2 1.4 Comparative Example 1 - Not measurable (Specimen breakage during test) Comparative Example 2 - No specimen production (liquid) Comparative Example 3 0.6 Comparative Example 4 0.5 Comparative Example 5 - Not measurable (Specimen breakage during test)

Referring to the results of Table 1, the sulfur-containing polymers of Examples 1 and 2 obtained by the method according to one embodiment of the present invention have a glass transition temperature of 60 ° C or higher, specifically 60 ° C to 75 ° C Of the total. On the other hand, in Comparative Examples 1 to 5, only one of the first aromatic compound and the second aromatic compound was used, or an annealing process was not performed during the manufacturing process, 1 &amp; cir &amp; &amp; tilde &amp; 2 &amp; cir &amp; That is, the polymers of Comparative Examples 1 to 5 have lower thermal stability and inferior post-processability than the polymers of Examples 1 and 2.

Also, referring to the results of Tables 2 and 3, the sulfur-containing polymers of Examples 1 and 2 obtained by the method according to one embodiment of the present invention and having a glass transition temperature of 60 ° C or higher have a refractive index of 1.740 to 1.760 , And the transmittance of the infrared (mid-IR) of 5 탆 is 70% or more, specifically 70% to 75%, and the modulus is 1.4 GPa or more, specifically 1.4 GPa to 1.5 GPa. On the other hand, in Comparative Examples 1 to 5, in which the glass transition temperature is lower than 60 占 폚 or even impossible to be measured, the refractive index does not fall within the range of 1.740 to 1.760, the mid-IR transmittance of 5 占 퐉 is less than 70% And modulus of less than 1.0 GPa, which is lower than that of the polymers of Examples 1 and 2 and poor in heat resistance.

Claims (13)

Sulfur element; A first aromatic compound having one vinyl group; And a second aromatic compound having two vinyl groups as constitutional units,
When the glass transition temperature (Tg) is 60 占 폚 or higher
Sulfur containing polymer.
The method according to claim 1,
Wherein the sulfur element comprises 40 wt% to 70 wt%
Sulfur containing polymer.
The method according to claim 1,
Wherein the weight ratio of the first aromatic compound to the second aromatic compound is from 10:60 to 30:20
Sulfur containing polymer.
The method according to claim 1,
Wherein the first aromatic compound comprises at least one of compounds represented by the following general formula
Sulfur-containing polymer:
[Chemical Formula 1]

In Formula 1,
Each R independently represents an alkyl group having 1 to 10 carbon atoms, an amino group, an alkylamino group having 1 to 10 carbon atoms, a halogen group or an alkyl halide group having 1 to 10 carbon atoms,
n is an integer of 0 to 5;
The method according to claim 1,
Wherein the second aromatic compound is selected from the group consisting of 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, Containing one
Sulfur containing polymer.
The method according to claim 1,
A refractive index of 1.650 to 1.870,
A transmittance of 40% to 90% with respect to infrared (mid-IR) at a wavelength of 3 탆 to 5 탆,
Modulus of 1.2 GPa to 1.8 GPa
Sulfur containing polymer.
The method according to claim 1,
With the application of the infrared (mid-IR) transmission lens
Sulfur containing polymer.
(a) a sulfur-containing feedstock, a first aromatic compound having one vinyl group; And a second aromatic compound having two vinyl groups while heating to prepare a mixture;
(b) stirring the mixture while heating; And
(c) annealing the mixture. &lt; RTI ID = 0.0 &gt;
(Method for producing sulfur - containing polymer).
9. The method of claim 8,
The sulfur feedstock is a sulfur compound of the S ₈ structure
(Method for producing sulfur - containing polymer).
9. The method of claim 8,
Wherein the step (a) is performed at 110 ° C to 200 ° C,
(a1) mixing the sulfur feedstock and the first aromatic compound with each other,
(a2) mixing the second aromatic compound
(Method for producing sulfur - containing polymer).
9. The method of claim 8,
The step (b) is carried out at a temperature of 110 ° C to 200 ° C and a stirring speed of 200 rpm to 500 rpm
(Method for producing sulfur - containing polymer).
9. The method of claim 8,
Wherein step (b) comprises stirring the mixture until the viscosity of the mixture reaches 1,000,000 cps to 20,000,000 cps
(Method for producing sulfur - containing polymer).
9. The method of claim 8,
Wherein the step (c) comprises: placing the mixture at 90 to 130 DEG C for 24 to 60 hours, followed by cooling at room temperature
(Method for producing sulfur - containing polymer).