KR102443090B1 - Polymer Film Using sCVD, Method and Apparatus of Preparing the Same - Google Patents

Abstract

The present invention relates to a method for producing a polymer film using chemical vapor deposition (sCVD) using sulfur as an initiator to prepare a polymer film through polymer polymerization of sulfur and a monomer using sulfur in gaseous state as an initiator, wherein the prepared polymer film comprises: Various monomers can be polymerized with sulfur and a copolymer, and a polymer film having a high sulfur content and excellent refractive index and transparency can be prepared.

Description

Polymer Film Using sCVD, Method and Apparatus of Preparing the Same

The present invention relates to a polymer film using chemical vapor deposition (sCVD) using sulfur as an initiator, a method for manufacturing the same, and a manufacturing apparatus, and more particularly, sulfur and various monomers are well mixed by using sulfur in a gaseous state as an initiator, It relates to a polymer film using chemical vapor deposition (sCVD) using sulfur as an initiator for producing a polymer film having excellent refractive index and transparency by depositing a polymer through polymer polymerization, a method for manufacturing the same, and an apparatus for manufacturing the same.

Elemental sulfur has a very abundant amount that is generated about 6 million tons worldwide during the crude oil refining process. is indicating Despite the abundant amount of sulfur and excellent physical properties, it has limitations in practical application due to two major problems. The first is the machinability problem. Sulfur becomes a thermoplastic material when it is heated to 160 ^o C or higher and melted in a liquid phase, but when it cools down at a lower temperature, it becomes brittle and rough again, and it has very low solubility, which makes it difficult in the processing process. The second is stability. In sulfur, eight sulfur elements form a ring structure, and this structure is in a very stable state, indicating a phenomenon in which it returns to the S ₈ form even after processing. There is a need for a method to solve this problem and reduce sulfur to a high-value material.

Recently, as a method of recycling elemental sulfur, a new method called inverse vulcanization has been proposed. A sulfur-based plastic material having a network structure having a high sulfur content was obtained by heating sulfur to 160 ^o C or higher to radicalize it in a liquid phase, and mixing it with a liquid monomer. By polymerizing the cross-linked polymer, a plastic in a stable form was developed rather than the brittle nature of sulfur even after cooling. Through this, we succeeded in synthesizing sulfur polymers that can be used in various fields such as optical lenses, Li-S batteries, and heavy metal adsorption, and were disclosed in related patents and various journals (US Patent Publication No. US20140199592; Chung, Woo Jin, et al., Nature chemistry 5.6 (2013): 518-524; Griebel, Jared J., et al.; Advanced Materials 26.19 (2014): 3014-3018). In the referenced prior art, diisopropenylbenzene (DIB) was used as a monomer, and a sulfur polymer having a sulfur content of 70% or more was successfully synthesized. By using this, the performance of the Li-S battery was improved, and it was used to manufacture a lens with high transparency and refractive index in the IR region. However, the biggest problem of the previous research is that it is possible only when liquid sulfur and monomer are mixed in the process, the long-term stability of the sulfur bond in the synthesized sulfur polymer is long, so the long-term stability is not good, and the color due to absorption of wavelengths in the visible ray region is It has a limit to apply to various applications because it is yellow, so it needs improvement.

Accordingly, the present inventors have made diligent efforts to solve the above problems, and as a result, a polymer film is produced by depositing a polymer through polymer polymerization of sulfur and monomer using the sCVD process, which is a chemical vapor deposition process using sulfur in gaseous state as an initiator. , a polymer having a short sulfur bond length, which can be polymerized with a monomer having low miscibility with sulfur, was synthesized. As a result, it was confirmed that a polymer having a very high refractive index and transparency could be prepared, and the present invention was completed.

An object of the present invention is to use chemical vapor deposition (sCVD) using sulfur as an initiator, which does not contain unreacted sulfur, mixes well with monomers and sulfur, has a short sulfur bond length, and can produce a polymer having a very high refractive index and transparency. An object of the present invention is to provide a method for manufacturing a polymer membrane, a polymer membrane prepared by the method, and an apparatus for manufacturing the same.

In order to achieve the above object, the present invention comprises the steps of (a) introducing a monomer in a gaseous state and sulfur in a solid state into an sCVD reactor; (b) heating and vaporizing sulfur in a solid state to mix sulfur in a gaseous state and a monomer; and (c) heating the substrate to adsorb and polymerize sulfur and monomer on the substrate to deposit a sulfur-containing polymer. It provides a method for producing a polymer film using chemical vapor deposition (sCVD) using sulfur as an initiator. .

In addition, the present invention has a refractive index of 1.7 to 1.9 and a transparency of 90 to 99.9% in the visible region, a sulfur content of 60 to 80 wt%, a sulfur bond length of 2.0 to 8.0, and poly(sulfur-co-1,4) -Butanediol divinyl ether) (poly(sulfur-co-1,4-butanediol divinyl ether, SBDDVE), poly(sulfur-co-di(ethylene glycol) divinyl ether) (poly(sulfur-co-di(ethylene glycol) ) divinyl ether, SDEGDVE), poly(sulfur-co-divinyl benzene) (poly(sulfur-co-divinyl benzene, SDVB), poly(sulfur-co-1,9-decadiene) (poly(sulfur-co) -1,9-decadiene, SDDE), poly(sulfur-co-1,11-dodecadiene) (poly(sulfur-co-1,11-dodecadiene, SDDDE), poly(sulfur-co-1,3) ,5-trivinyl-1,3,5-trimethylcyclotrisiloxane) (poly(sulfur-co-1,3,5-trivinyl-1,3,5-trimethyl cyclotrisiloxane, SV3D3), poly(sulfur-co- 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane) (poly(sulfur-co-1,3,5,7-tetravinyl-1,3,5,7- One type of sulfur copolymer selected from the group consisting of tetramethylcyclotetrasiloxane, SV4D4) and poly(sulfur-co-hexavinyldisiloxane, SHVDS) is coated with a thickness of 1 nm to 10 μm. It provides a polymer film of a sulfur-containing copolymer.

In addition, the present invention (a) sCVD reactor (10); (b) a sulfur loading source cell 100 that is installed at the bottom of the sCVD reactor 10 and can load solid sulfur inside the reactor 10, and is heated during the process to evaporate sulfur; (c) a monomer loading unit 200 connected to the top of the sCVD reactor 10, heating the introduced monomer to have a sufficient vapor pressure, and then moving the vapor phase monomer into the sCVD reactor 10; (d) a filament 300 made of a high-temperature metal alloy wire to shorten the bonding length of vapor-phase sulfur evaporated from the sulfur-loading source cell 100, and to allow the vaporized sulfur to move to the substrate 400; And (e) the upper surface is mounted to face the lower portion of the sCVD reactor 10, and then the monomer moved from the monomer loading unit 200 of (b) into the sCVD reactor 10 is adsorbed on the upper surface, and evaporated Provided is an apparatus (1) for manufacturing a polymer film using chemical vapor deposition (sCVD) using sulfur as an initiator, including a substrate (400) on which a synthesis reaction of sulfur and polymer is performed.

In the method for producing a polymer film using sCVD according to the present invention, unlike the conventional reverse vulcanization reaction in a liquid state, there is no risk of phase separation because the monomer and sulfur radicals are mixed in the gas phase, and various monomers are mixed with sulfur and air. Polymerization is possible by coalescence, and various polymers can be synthesized by flowing two or more types of monomers together. Furthermore, by using sulfur not only as an initiator, but also as a copolymer unit in polymer polymerization, it is possible to produce a polymer having a high sulfur content when deposited together with a cross-linkable monomer.

In addition, by injecting sulfur and monomers into a vacuum chamber in a vapor phase, a polymer having a high sulfur content can be deposited using various monomers, and a transparent sulfur polymer can be synthesized. This can be newly applied to various fields such as existing batteries, lenses, and insulating films.

1 is a view schematically showing a schematic diagram of an sCVD process according to an embodiment of the present invention.
Figure 2a is a view showing a SEM & EDS cross-sectional image (a) and AFM image (b) in which SBDDVE is deposited on a nylon mesh according to an embodiment of the present invention.
2B is a list of monomers used in sCVD according to an embodiment of the present invention.
3 is a view showing the FT-IR, XPS analysis results of the sulfur copolymer synthesized by sCVD according to an embodiment of the present invention.
4 is a graph showing the sulfur bond length in the polymer through the XPS analysis result of the sulfur copolymer synthesized by sCVD according to an embodiment of the present invention.
5 is a view showing the XRD, DSC, TGA analysis results of the sulfur copolymer synthesized by sCVD according to an embodiment of the present invention.
6 is a graph (right) of the refractive index and extinction coefficient (left), transparency (middle), thickness vs average refractive index (average refractive index value of 400 nm to 700 nm) of the sulfur copolymer synthesized by sCVD according to an embodiment of the present invention. .
7 is a cross-sectional view of an apparatus 1 for manufacturing a polymer film using chemical vapor deposition (sCVD) using sulfur as an initiator according to an embodiment of the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is those well known and commonly used in the art.

In the present invention, when a polymer film is prepared by depositing a polymer through polymer polymerization of sulfur and monomer using the sCVD process, which is a chemical vapor deposition process using sulfur in gaseous state as an initiator, polymerization is possible even with a monomer with low miscibility. It was confirmed that a polymer having a very high refractive index and transparency can be prepared by having a short sulfur bond.

Accordingly, the present invention in one aspect, (a) introducing a monomer in a gaseous state and sulfur in a solid state into the sCVD reactor; (b) heating and vaporizing sulfur in a solid state to mix sulfur in a gaseous state and a monomer; and (c) heating the substrate to adsorb and polymerize sulfur and monomers on the substrate to deposit a sulfur-containing polymer. It relates to a method for producing a polymer film using chemical vapor deposition (sCVD) using sulfur as an initiator. .

In addition, in another aspect of the present invention, it has a refractive index of 1.7 to 1.9 and a transparency of 90% or more in the visible region, the sulfur content is 60 to 80 wt%, the sulfur bond length is 2.0 to 8.0, and poly(sulfur-co-1) ,4-butanediol divinyl ether) (poly (sulfur-co-1,4-butanediol divinyl ether, SBDDVE), poly (sulfur-co-di (ethylene glycol) divinyl ether) (poly (sulfur-co-di ( ethylene glycol) divinyl ether, SDEGDVE), poly(sulfur-co-divinyl benzene) (poly(sulfur-co-divinyl benzene, SDVB), poly(sulfur-co-1,9-decadiene) (poly(sulfur) -co-1,9-decadiene, SDDE), poly(sulfur-co-1,11-dodecadiene) (poly(sulfur-co-1,11-dodecadiene, SDDDE), poly(sulfur-co-1) ,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane) (poly(sulfur-co-1,3,5-trivinyl-1,3,5-trimethyl cyclotrisiloxane, SV3D3), poly(sulfur- co-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane) (poly(sulfur-co-1,3,5,7-tetravinyl-1,3,5, One type of sulfur copolymer selected from the group consisting of 7-tetramethylcyclotetrasiloxane, SV4D4) and poly(sulfur-co-hexavinyldisiloxane, SHVDS) is coated with a thickness of 10 nm to 2 μm. It relates to a polymer film of a sulfur-containing copolymer characterized in that.

In the present invention, by mixing gaseous sulfur and monomer together in the chamber, polymer deposition in the gas phase was successful without an initiator. Unlike the existing liquid phase process, since it is a gas phase process that mixes sulfur in a vacuum with a monomer in a gas phase, it is possible to polymerize various monomers that do not mix with liquid sulfur into a polymer, and it can be applied to various substrates without damage when depositing a thin polymer film do. In addition, very thin thin films can be manufactured, and deposition is possible in complex structures that are impossible in the liquid phase process.

In the present invention, in order to process sulfur to synthesize various polymer materials, it is characterized in that polymer polymerization is performed using sulfur in a gaseous state. 1 shows an overall schematic diagram and reaction scheme of a chemical vapor deposition (sCVD) process using sulfur as an initiator. It is used as an initiator for initiating polymer polymerization by heating sulfur existing in a ring state at room temperature to vaporize it, causing ring opening to change it into a linear sulfur in a radical state. Unlike the conventional inverse vulcanization reaction in the liquid phase, since the monomer and the sulfur radical are mixed in the gas phase, there is no risk of phase separation, which is a great advantage. Therefore, it is possible to polymerize various monomers with sulfur and a copolymer, and by flowing two or more types of monomers together, various polymers can be synthesized. Furthermore, by using sulfur as a copolymer unit in polymer polymerization rather than simply serving as an initiator, it is possible to produce a polymer having a high sulfur content when deposited with a cross-linkable monomer.

As shown in FIG. 2a , a conformal film was formed even in a nano-sized pattern, and it was confirmed that a very flat film was synthesized through AFM analysis. As other methods using vapor deposition such as chemical vapor deposition (iCVD) and atomic layer deposition (ALD) using initiators can deposit uniform thin films on 3D substrates with various structures, sCVD can also utilize the advantages of vapor deposition. means

Figure 2b is a summary of the monomers successfully synthesized in the present invention by series. Butanediol divinyl ether (BDDVE), di (ethylene glycol) divinyl ether (di(ethylene glycol) divinyl ether, DEGDVE), divinylbenzene (DVB), 1,9-decadiene (1) ,9-decadiene, DDE), 1,11-dodecadiene (1,11-dodecadiene, DDDE), 1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane (1,3, 5-trimethyl-1,3,5-trivinyl cyclotrisiloxane (V3D3), 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (1,3,5,7-tetravinyl Various successful sulfur copolymers were synthesized using -1,3,5,7-tetramethylcyclotetrasiloxane (V4D4) or hexavinyldisiloxane (HVDS), and a thin film-type polymer was successfully deposited. The synthesized polymer was named as follows: poly(sulfur-co-1,4-butanediol divinyl ether) (poly(sulfur-co-1,4-butanediol divinyl ether, SBDDVE), poly(sulfur-co-divinyl ether) (ethylene glycol) divinyl ether) (poly(sulfur-co-di(ethylene glycol) divinyl ether, SDEGDVE), poly(sulfur-co-divinyl benzene) (poly(sulfur-co-divinyl benzene, SDVB), poly (sulfur-co-1,9-decadiene) (poly(sulfur-co-1,9-decadiene, SDDE), poly(sulfur-co-1,11-dodecadiene) (poly(sulfur-co) -1,11-dodecadiene, SDDDE), poly (sulfur-co-1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane) (poly (sulfur-co-1,3,5-trivinyl) -1,3,5-trimethyl cyclotrisiloxane, SV3D3), poly(sulfur-co-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane) (poly(sulfur-co) -1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (SV4D4) and poly(sulfur-co-hexavinyldisiloxane, SHVDS). In particular, the monomers used are It is a cross-linked polymer capable of cross-linking a network structure when two or more vinyl groups are combined with sulfur.

For polymer deposition, the monomer is heated and introduced into a vacuum chamber in a gaseous state, and at the same time, sulfur in a solid state is heated in the chamber to vaporize, thereby mixing sulfur and two kinds of gases in the vapor phase. By heating the filament hot inside the chamber, the vaporized sulfur can better generate radicals, and by heating the target substrate to about 110 ~ 130 ° C, which is relatively lower than other parts, sulfur and monomers are adsorbed to cause polymer polymerization.

In the present invention, the polymer is poly(sulfur-co-1,4-butanediol divinyl ether) (poly(sulfur-co-1,4-butanediol divinyl ether, SBDDVE), poly(sulfur-co-di(ethylene) glycol) divinyl ether) (poly(sulfur-co-di(ethylene glycol)divinyl ether, SDEGDVE), poly(sulfur-co-divinyl benzene) (poly(sulfur-co-divinyl benzene, SDVB), poly(sulfur) -co-1,9-decadiene) (poly(sulfur-co-1,9-decadiene, SDDE), poly(sulfur-co-1,11-dodecadiene) (poly(sulfur-co-1) ,11-dodecadiene, SDDDE), poly(sulfur-co-1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane) (poly(sulfur-co-1,3,5-trivinyl-1) ,3,5-trimethyl cyclotrisiloxane, SV3D3), poly(sulfur-co-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane) (poly(sulfur-co-1) ,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (SV4D4) or poly(sulfur-co-hexavinyldisiloxane, SHVDS).

The process may be performed for 5 minutes to 2 hours at a substrate temperature of 90 ~ 140 ℃, preferably at a temperature of 110 ~ 130 ℃ and a pressure of 500 ~ 1500 mTorr. At this time, if the temperature is less than 90 ℃, it may be deposited foggy, and if it exceeds 140 ℃, there is a problem that the reactant is not adsorbed and there is a problem that the film is not formed, and the pressure of the chamber in the reactor is less than 500 mTorr or exceeds 1500 mTorr In this case, there is a problem in that deposition is not made or the deposited film is dirty. and. The amount of sulfur is proportional to the deposition thickness, and there is a problem in that recrystallization occurs in the film depending on the reaction conditions.

In addition, in the present invention, it may further include the step of heating the filament inside the reactor to a temperature of 330 ~ 380 ℃ after step (b). In addition, in step (c), the substrate may be heated to a temperature of 110 to 130 °C.

In the present invention, the monomer is a monomer having a vinyl group, butanediol divinyl ether (BDDVE), di(ethylene glycol) divinyl ether (di(ethylene glycol) divinyl ether, DEGDVE), divinylbenzene ( divinylbenzene, DVB), 1,9-decadiene (1,9-decadiene, DDE), 1,11-dodecadiene (1,11-dodecadiene, DDDE), 1,3,5-trimethyl-1, 3,5-trivinyl cyclotrisiloxane (1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane, V3D3), 1,3,5,7-tetravinyl-1,3,5,7-tetra At least one selected from the group consisting of methylcyclotetrasiloxane (1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, V4D4) and hexavinyldisiloxane (HVDS) is used, The present invention is not limited thereto.

In step (a), the thickness and refractive index increase in proportion to the amount of sulfur introduced in step (a).

The thickness of the polymer can be controlled within 10nm ~ 2㎛.

The substrate is a silicon wafer, glass, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polydimethyl siloxane (PDMS), polyimide (polyimide, PI), latex, porous stainless steel mesh, polyacrylonitrile, polydimethylsiloxane, polyethersulfone (PES), polysulfone (PSF) And it may be one selected from the group consisting of polyvinylidene fluoride (poly(vinylidenedifluoride), PVDF).

3 shows the FT-IR and XPS analysis results of the sulfur copolymer synthesized by sCVD. In FT-IR, absorption peaks of the monomer, the polymer deposited by iCVD, and the polymer deposited by sCVD were compared. However, BDDVE, DEGDVE, DDE, and DDDE were excluded because they could not be deposited by iCVD because they were materials that did not undergo homo-polymerization. The functional groups of the monomers, iCVD-deposited polymers, and sCVD-deposited polymers were all well observed, and only the sCVD-deposited polymer showed an SS stretching peak near 480 cm ^-1 and 1080 cm ^-1 at A CS stretching peak was observed. This means that all monomers were successfully reacted with sulfur through the sCVD process. Through XPS analysis, the binding state was confirmed through quantitative analysis of the constituent elements of the SBDDVE polymer synthesized by sCVD and high-resolution measurement of each element. CCO, CCC, CCS, and OCS peaks were confirmed in the C 1s peak and O 1s peak, which means that the polymer was synthesized without damage to the monomer of BDDVE. Through high-resolution measurement of the S 2p peak, it was confirmed that the SS bond and the SC bond coexist. From the FT-IR and XPS results, it can be confirmed that the components of the polymer thin film are made through chemical bonding of sulfur and monomers, rather than self-deposition due to monomer denaturation or heat.

In the present invention, the sulfur bond length (sulfur rank) does not mean the length of the sulfur bond itself, but means the number of sulfur bonds in the bond connecting the monomer and the monomer in the polymer (no unit), preferably Preferably in the range of 2.0 to 8.0, more preferably in the range of 3.0 to 7.5.

4 shows the sulfur bond length in the polymer polymerized by sCVD calculated through the XPS analysis result and the S2p high-resolution graph. When the S2p high-resolution graph was deconvolved, the polymer C-S/S-S ratio could be obtained, and the sulfur bond length in the polymer could be calculated through this. (From S2p) Also, assuming that one vinyl group forms two C-S bonds and there is no vinyl group remaining in the monomer after polymerization, the average sulfur bond length in the polymer can be calculated through the element ratio (From survey). It can be seen that there is little difference between the sulfur bond length calculated through deconvolution and the sulfur bond length calculated through the element ratio, which means that almost no unreacted vinyl groups remain in the synthesized polymer assumed above. , which means that the formed sulfur bond length is short and shows a high degree of crosslinking. Through this, it shows that the problem of low long-term stability and color appearance due to a long bond length, which was a problem in the inverse vulcanization reaction, can be solved through the sCVD process developed in the present invention.

5 is an XRD, TGA, AFM, DSC analysis result of a sulfur copolymer synthesized by sCVD. In XRD analysis, sulfur has crystallinity and shows a crystalline peak at a specific angle, whereas SBDDVE synthesized by sCVD has no crystallinity at all angles and exhibits amorphous properties. In the DSC results, it was confirmed that sulfur has a melting point at 110 °C to 130 °C, so a peak absorbing heat appears, but in the case of SBDDVE synthesized by sCVD, the corresponding peak does not appear. In addition, the Tg value also shows a very high value compared to sulfur having around -30 ℃. In the TGA result, 300 for sulfur ℃ and 400 It is all decomposed at ℃ and the mass % reaches 0%, but in the case of SBDDVE, it is 500 It can be seen that the mass % remains even at ℃ or higher. This means that all SS bonds are cleaved, but CC/CS bonds remain. These three analysis results indicate that unreacted sulfur does not exist in the sulfur polymer synthesized by sCVD, and the reactants form a good bond with the monomers.

In the present invention, from the results of analyzing the optical properties of the polymer synthesized by sCVD, it can be seen that the polymer synthesized by sCVD has a very high refractive index as a polymer material and hardly absorbs light in the visible ray region. In fact, when the transparency was measured even at a thickness of 1 μm or more, it was confirmed that the transparency was 90% or more. This is a characteristic different from the conventional sulfur polymer synthesized by reverse curing, and is expected to appear as a characteristic that is homogenously mixed in the gas phase. Transparency may have a transparency of 90% or more, preferably 90 to 99.9%.

In addition, the refractive index and thickness can be adjusted through the sCVD process. In the case of the refractive index, it has a very high value for a polymer material from the early 1.7 to the early 1.9 range, but there is no transparent polymer material having a refractive index in the corresponding range until now.

In the present invention, a polymer having a high sulfur content can be deposited by injecting sulfur and a monomer into a vacuum chamber as a gaseous phase. These technologies are expected to be newly applied to various fields such as existing batteries, lenses, and insulating films.

In the present invention, as a result of designing as shown in FIG. 7 to synthesize a sulfur polymer, it was confirmed that the synthesis of a sulfur polymer with excellent physical properties was possible as a result of manufacturing with a chemical vapor deposition equipment using sulfur as an initiator.

Accordingly, in another aspect of the present invention (a) an sCVD reactor (10); (b) a sulfur loading source cell 100 that is installed at the bottom of the sCVD reactor 10 and can load solid sulfur inside the reactor 10, and is heated during the process to evaporate sulfur; (c) a monomer loading unit 200 connected to the top of the sCVD reactor 10, heating the introduced monomer to have a sufficient vapor pressure, and then moving the vapor phase monomer into the sCVD reactor 10; (d) a filament 300 made of a high-temperature metal alloy wire to shorten the bonding length of vapor-phase sulfur evaporated from the sulfur-loading source cell 100, and to allow the vaporized sulfur to move to the substrate 400; And (e) the upper surface is mounted to face the lower portion of the sCVD reactor 10, and then the monomer moved from the monomer loading unit 200 of (b) into the sCVD reactor 10 is adsorbed on the upper surface, and evaporated It relates to an apparatus (1) for producing a polymer film using chemical vapor deposition (sCVD) using sulfur as an initiator, including a substrate (400) on which a synthesis reaction of sulfur and polymer is performed.

A chemical vapor deposition equipment using sulfur as an initiator for synthesizing the sulfur polymer is shown in FIG. 7 . The apparatus according to the present invention is mainly composed of four parts.

(A) Sulfur loading source cell (100)

This configuration is a part of the source cell for loading sulfur. In the system according to the present invention, up to 3 g of elemental sulfur can be loaded, and it is composed of a ceramic material to withstand high temperatures. A line heater is provided around the source cell, and the heater can control the temperature of the source cell. The heater used can also set the temperature increase rate, and can raise the temperature by up to 350°C. The heating rate and temperature affect the evaporation rate and amount of sulfur, and at an appropriate temperature increase rate and temperature, sulfur is uniformly transferred to the substrate, and the synthesis of a sulfur polymer with excellent physical properties occurs.

(B) monomer loading unit 200

It is a part that loads a monomer that will react with sulfur. The monomer is put in a small container made of SUS up to 30ml and used after being collected in the line from the reactor. A monomer having a lower vapor pressure than sulfur is used, and it is sufficiently heated using a heater to inject it into the reactor as a gaseous phase. The heating temperature is different for each monomer used, and it is heated in the range of 20~120℃. A ball valve and a needle valve are provided above the connection line with the sCVD reactor 10 .

In order to prevent the adsorption of the vaporized monomers on the line connecting the reactor and the monomer gathering site, the line from the collected portion to the reactor is also heated in the range of 80-110°C using a heater. A baratron sensor is provided inside the sCVD reactor 10 to set the injection amount of the monomer by the pressure measured by the sensor.

(C) filament (300)

The filament is a part through which the vaporized sulfur passes, and was constructed using a Cr/Ni wire. The temperature of the filament can be heated up to 400°C. The filament shortens the bonding length of vapor phase sulfur evaporated from the sulfur loading source cell 100 . In addition, the height of the filament (the distance between the sulfur source cell and the substrate) can be flexibly adjusted in this equipment, and the synthesis of sulfur polymer with excellent physical properties occurs at an appropriate location.

(D) substrate 400

In general, SUS board is used for 10*10, and it can be removed and attached in this equipment. After fixing the target material to the substrate, the equipment is configured in such a way that the substrate is mounted facing down. The position of the mounted substrate can also be flexibly adjusted in the same way as the filament, and is designed to be rotatable. Sulfur evaporated from the source cell below can be uniformly deposited through substrate rotation, and through this, a sulfur polymer with excellent physical properties can be synthesized.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples.

[Example]

Preparation Example 1: Preparation of poly(sulfur-co-1,4-butanediol divinyl ether) (poly(sulfur-co-1,4-butanediol divinyl ether, SBDDVE) through sCVD)

10 ml of butanediol divinyl ether (BDDVE), a monomer, is heated to 60°C and introduced into a vacuum chamber in a gaseous state, and at the same time, 0.01 g to 1.5 g of solid sulfur is heated to 180° C. The gases of two types of monomers were mixed in the gas phase. By heating the filament hot (350℃) inside the chamber, the vaporized sulfur was better able to generate radicals, and the target substrate was heated to 110~130. A polymer film on which SBDDVE was deposited was prepared by heating to about ℃ to polymerize sulfur and monomers. The internal pressure of the chamber was maintained at 500-1500 mTorr.

Preparation Example 2: Preparation of poly(sulfur-co-di(ethylene glycol)divinyl ether) (poly(sulfur-co-di(ethylene glycol)divinyl ether, SDEGDVE)

It was carried out in the same manner as in Preparation Example 1, except that in Preparation Example 1, a polymer film on which SDEGDVE was deposited was prepared using di(ethylene glycol) divinyl ether (DEGDVE) as a monomer.

Preparation Example 3: Preparation of poly(sulfur-co-divinyl benzene) (poly(sulfur-co-divinyl benzene, SDVB)

The same procedure as in Preparation Example 1 was performed except that a polymer film on which SDVB was deposited was prepared using divinylbenzene (DVB) as a monomer in Preparation Example 1.

Preparation Example 4: Preparation of poly(sulfur-co-1,9-decadiene) (poly(sulfur-co-1,9-decadiene, SDDE)

It was carried out in the same manner as in Preparation Example 1, except that in Preparation Example 1, a polymer film on which SDVB was deposited was prepared using 1,9-decadiene (DDE) as a monomer.

Preparation Example 5: Preparation of poly(sulfur-co-1,11-dodecadiene) (poly(sulfur-co-1,11-dodecadiene, SDDDE)

It was carried out in the same manner as in Preparation Example 1, except that a polymer film on which SDVB was deposited was prepared using 1,11-dodecadiene (DDDE) as a monomer in Preparation Example 1

Preparation 6: poly(sulfur-co-1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane) (poly(sulfur-co-1,3,5-trivinyl-1,3,5) Preparation of -trimethyl cyclotrisiloxane, SV3D3)

The same procedure as in Preparation Example 1 was performed except that in Preparation Example 1, a polymer film on which SV3D3 was deposited was prepared using 1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane (V3D3) as a monomer. did.

Preparation 7: poly(sulfur-co-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane) (poly(sulfur-co-1,3,5,7-) Preparation of tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (SV4D4)

Preparation Example except that a polymer film on which SV4D4 was deposited was prepared using 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (V4D4) as a monomer in Preparation Example 1 1 was carried out in the same manner.

Preparation 8: Preparation of poly(sulfur-co-hexavinyldisiloxane, SHVDS)

It was carried out in the same manner as in Preparation Example 1, except that in Preparation Example 1, a polymer film on which SHVDS was deposited was prepared using hexabenyldisiloxane (HVDS) as a monomer.

Comparative Example 1 : Preparation of poly(divinyl benzene) (poly(divinyl benzene, pDVB)) through iCVD

Polymerization was carried out using the monomer divinyl benzene (divinyl benzene, DVB, 99%, Aldrich, USA) initiator tert-butyl peroxide (TBPO, 98%, Aldrich, USA). Monomers and initiators were used without purification. The vaporized monomer and initiator were injected into an iCVD reactor (Daeki Hi-Tech Co., Ltd). To obtain a vapor flow, the TBPO was maintained at room temperature and the DVB was heated to 40 degrees.

The input rates of DVB and TBPO were set to 1.679 and 0.613 sccm, respectively, and the reactor pressure and substrate temperature were maintained at 250 mtorr and 38°C. The filament temperature was set to 140°C.

Comparative Example 2 : Poly(1,3,5-trivinyl-1,3,5-trimethylcyclosiloxane) by iCVD (poly(1,3,5-trivinyl-1,3,5-trimethyl cyclotrisiloxane), pV3D3 ) manufacturing

iCVD to prepare poly(1,3,5-trivinyl-1,3,5-trimethylcyclosiloxane) (poly(1,3,5-trivinyl-1,3,5-trimethyl cyclotrisiloxane, pV3D3)) polymer In order to obtain a vapor flow of V3D3 and TBPO in the reactor, TBPO was maintained at room temperature and V3D3 was heated to 40° C., and the input rates were set to 4.12 and 1.61 sccm, respectively. The coagulation pressure and substrate temperature were maintained at 300 mtorr and 40°C. The filament temperature was set at 140°C.

Comparative Example 3 : Poly(1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane) via iCVD (poly(1,3,5,7-tetravinyl-1,3) Preparation of ,5,7-tetramethylcyclotetrasiloxane), pV4D4)

poly(1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane) ) To obtain the vapor flow of V4D4 and TBPO in the iCVD reactor to prepare the polymer, TBPO was maintained at room temperature and V4D4 was heated to 70° C., and the feed rate was set to 0.93 and 0.67 sccm, respectively. The coagulation pressure and substrate temperature were maintained at 145 mtorr and 40°C. The filament temperature was set at 140°C.

Comparative Example 4 : Preparation of poly (hexavinyldisiloxane, pHVDS) through iCVD

To obtain a vapor flow of HVDS and TBPO in an iCVD reactor to prepare poly(hexavinyldisiloxane, pHVDS) polymer, TBPO was maintained at room temperature and HVDS was heated to 40 °C, and the input rate was 0.99, respectively. and 0.74 sccm The coagulation pressure and substrate temperature were maintained at 200 mtorr and 30° C. The filament temperature was set at 140° C.

Example 1: Analysis of polymers prepared using sCVD and iCVD

2 is an AFM analysis result of a film synthesized by sCVD. The phase image shows that the film is well synthesized without phase separation. It can be seen from the height image that a very flat film was formed with a low surface roughness of 0.365 nm. 3 is a result of FT-IR and XPS analysis of a sulfur copolymer synthesized by sCVD. In FT-IR, absorption peaks of the monomer, the polymer deposited by iCVD, and the polymer deposited by sCVD were compared. However, BDDVE, DEGDVE, DDE, and DDDE were excluded because they could not be deposited by iCVD because they were materials that did not undergo homo-polymerization. Monomer, iCVD-deposited polymer, and sCVD-deposited polymer showed the functional groups of each monomer well observed, and only the sCVD-deposited polymer showed an SS stretching peak near 480 cm ^-1 and 1080 cm ^-1 at A CS stretching peak was observed. This means that all monomers were successfully reacted with sulfur through the sCVD process. Through XPS analysis, the binding state was confirmed through quantitative analysis of constituent elements of the SBDDVE polymer synthesized by sCVD and high-resolution measurement of each element. CCO, CCC, CCS, and OCS peaks were confirmed in the C 1s peak and O 1s peak, which means that the polymer was synthesized without damage to the monomer of BDDVE. Through high-resolution measurement of the S 2p peak, it was confirmed that the SS bond and the SC bond coexist. Through the FT-IR and XPS results, it can be confirmed that the components of the polymer thin film are made through chemical bonding of sulfur and monomers, not by self-deposition by heat or denaturation of monomers.

Example 2: Analysis of Sulfur Bond Length of Polymers Prepared Using sCVD

4 shows the sulfur bond length in the polymer polymerized by sCVD calculated through the XPS analysis result and the S2p high-resolution graph. When the S2p high-resolution graph was deconvolved, the polymer C-S/S-S ratio was obtained, and the length of the sulfur bond in the polymer can be calculated through this (From S2p). In addition, one vinyl group forms two C-S bonds, , assuming that there is no vinyl group remaining in the monomer after polymerization, the average sulfur bond length in the polymer can be calculated through the element ratio (From survey). It can be seen that there is little difference between the sulfur bond length calculated through deconvolution and the sulfur bond length calculated through the element ratio, which means that almost no unreacted vinyl groups remain in the synthesized polymer assumed above. , which means that the formed sulfur bond length is short and shows a high degree of crosslinking. Through this, it shows that the problem of low long-term stability and color appearance due to a long bond length, which was a problem in the inverse vulcanization reaction, can be solved through the sCVD process developed in the present invention.

Example 3: Crystallinity Analysis of Polymers Prepared Using sCVD

5 is an XRD, TGA, DSC analysis result of a sulfur copolymer synthesized by sCVD. In XRD analysis, sulfur has crystallinity and shows a crystalline peak at a specific angle, whereas SBDDVE synthesized by sCVD has no crystallinity at all angles and exhibits amorphous properties. In the DSC results, it was confirmed that sulfur has a melting point at 110°C to 130°C, so a peak absorbing heat appears, but in the case of SBDDVE synthesized by sCVD, the corresponding peak does not appear. In addition, the Tg value also shows a very high value compared to sulfur having around -30 ℃. In the TGA result, 300 for sulfur ℃ and 400 It all decomposes at °C and the mass % reaches 0%, but in the case of SBDDVE it is 500 It can be seen that the mass % remains even at ℃ or higher. This means that all SS bonds are cleaved, but CC/CS bonds remain. These three analysis results indicate that unreacted sulfur does not exist in the sulfur polymer synthesized by sCVD, and that the reactant forms a good bond with the monomer.

Example 4: Analysis of optical properties of polymers prepared using sCVD

6 shows the optical properties of the polymer synthesized by sCVD. The polymer synthesized by sCVD has a very high refractive index as a polymer material, and shows little absorption in the visible region. In fact, when the transparency was measured even at a thickness of 1 μm or more, it was confirmed that the transparency was 90% or more. This is a characteristic different from the conventional sulfur polymer synthesized by reverse curing, and is expected to appear as a characteristic that is homogenously mixed in the gas phase. In addition, as can be seen from the graph on the right of FIG. 5 , the refractive index and thickness could be adjusted through the sCVD process. In the case of the refractive index, it is a very high value for a polymer material, from the early 1.7 to the late 1.9, and there is no transparent polymer material having a refractive index in the corresponding range until now.

As the specific parts of the present invention have been described in detail above, for those of ordinary skill in the art, it is clear that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. will be. Accordingly, it is intended that the substantial scope of the invention be defined by the claims and their equivalents.

1: sCVD manufacturing apparatus
10: sCVD reactor
100: sulfur loading source cell
200: monomer loading unit
300: filament
400: substrate

Claims (14)

A method for producing a polymer film using chemical vapor deposition (sCVD) using sulfur as an initiator, comprising the following steps:
(a) introducing a monomer in a gaseous state and sulfur in a solid state into the sCVD reactor;
(b) heating and vaporizing sulfur in a solid state to mix sulfur in a gaseous state and a monomer; and
(c) depositing a sulfur copolymer by heating the substrate to adsorb and polymerize sulfur and monomers on the substrate, wherein the polymer film has a refractive index of 1.7 to 1.9 and a transparency of 90 to 99.9% in the visible region, The content is 60~80wt%, the sulfur bond length is 2.0~8.0, poly(sulfur-co-1,4-butanediol divinyl ether (SBDDVE), poly(sulfur-co-di(ethylene glycol) divinyl ether) (SDEGDVE), poly(sulfur-co-divinyl benzene) (SDVB), poly(sulfur-co-1,9-decadiene) (poly(sulfur-co-1,9-decadiene, SDDE), poly( Sulfur-co-1,11-dodecadiene) (poly(sulfur-co-1,11-dodecadiene, SDDDE), poly(sulfur-co-1,3,5-trivinyl-1,3,5- trimethylcyclotrisiloxane) (SV3D3), poly(sulfur-co-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane) (SV4D4) and poly(sulfur-co- Characterized in that it is coated with one kind of sulfur copolymer selected from the group consisting of hexavinylsiloxane (SHVDS).
delete The method of claim 1, wherein the process is performed for 5 minutes to 2 hours at a substrate temperature of 90 to 140° C. and a pressure of 500 to 1500 mTorr.
The method of claim 1, further comprising heating the filament inside the reactor to a temperature of 330 to 380°C after step (b).
The method of claim 1, wherein in step (c), the substrate is heated to a temperature of 110 to 130 °C.
According to claim 1, wherein the monomer is butanediol divinyl ether (butanediol divinyl ether, BDDVE), di (ethylene glycol) divinyl ether (di (ethylene glycol) divinyl ether (DEGDVE), divinylbenzene (divinylbenzene, DVB), 1,9-decadiene (1,9-decadiene, DDE), 1,11-dodecadiene (1,11-dodecadiene, DDDE), 1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane (1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane, V3D3), 1,3,5,7-tetravinyl Group consisting of -1,3,5,7-tetramethylcyclotetrasiloxane (1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, V4D4) and hexavinyldisiloxane (HVDS) A method for producing a polymer membrane, characterized in that at least one selected from
The method of claim 1, wherein the thickness of the sulfur copolymer is 1 nm to 10 μm.
It has a refractive index of 1.7 to 1.9 and a transparency of 90 to 99.9% in the visible region, a sulfur content of 60 to 80 wt%, a sulfur bond length of 2.0 to 8.0, and poly(sulfur-co-1,4-butanediol divinyl ether). (SBDDVE), poly (sulfur-co-di(ethylene glycol) divinyl ether) (SDEGDVE), poly (sulfur-co-divinyl benzene) (SDVB), poly (sulfur-co-1,9-decadiene) ) (poly(sulfur-co-1,9-decadiene, SDDE), poly(sulfur-co-1,11-dodecadiene) (poly(sulfur-co-1,11-dodecadiene, SDDDE), poly( Sulfur-co-1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane) (SV3D3), poly(sulfur-co-1,3,5,7-tetravinyl-1,3,5) One type of sulfur copolymer selected from the group consisting of ,7-tetramethylcyclotetrasiloxane) (SV4D4) and poly(sulfur-co-hexavinylsiloxane (SHVDS) is coated with a thickness of 1 nm to 10 μm. A polymer film of a sulfur copolymer.
An apparatus (1) for producing a polymer film using chemical vapor deposition (sCVD) using sulfur as an initiator for carrying out the method of claim 1, comprising:
(a) an sCVD reactor 10;
(b) a sulfur loading source cell 100 that is installed at the bottom of the sCVD reactor 10 and can load solid sulfur inside the reactor 10, and is heated during the process to evaporate sulfur;
(c) a monomer loading unit connected to the top of the sCVD reactor 10, heated to inject the monomer into the gas phase, and then moved into the sCVD reactor 10 to have a process pressure in the range of 500 to 1500 mtorr;
(d) a filament 300 made of a high-temperature metal alloy wire to shorten the bonding length of vapor-phase sulfur evaporated from the sulfur-loading source cell 100, and to allow the vaporized sulfur to move to the substrate 400; and
(e) the upper surface is mounted to face the lower part of the sCVD reactor 10, and then the monomer moved from the monomer loading part 200 of (b) into the sCVD reactor 10 is adsorbed on the upper surface and evaporated A substrate 400 on which a synthesis reaction of sulfur and polymer is carried out.
10. The chemical vapor deposition (sCVD) using sulfur as an initiator according to claim 9, wherein a line heater for controlling the temperature and the temperature increase rate is provided around the sulfur-loading source cell 100 of (b). An apparatus for manufacturing a polymer membrane using (1).
10. The method according to claim 9, wherein a ball valve and a needle valve for controlling the flow rate of the monomer are provided above the connection line between the monomer loading part 200 and the sCVD reactor 10 of (c). An apparatus (1) for manufacturing a polymer film using chemical vapor deposition (sCVD) using sulfur as an initiator, characterized in that
10. The method of claim 9, wherein a baratron sensor for setting the injection amount of the monomer is provided inside the sCVD reactor (10). An apparatus for manufacturing a polymer membrane (1).
[10] The apparatus (1) of claim 9, wherein the substrate 400 of (e) is rotatable.
10. The method of claim 9, wherein the height of the filament 300 of (d) and the substrate 400 of (e) can be adjusted, respectively. Manufacturing apparatus (1).

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