KR101062923B1 - Vinyl Phosphate Polymer and Method for Making the Same - Google Patents

Abstract

The present invention is a polymer consisting of a vinyl phosphate monomer, having a weight average molecular weight of 100,000 to 500,000, a vinyl phosphate polymer and a vinyl phosphate monomer having an intrinsic viscosity of 2 to 20 dl / g in a 0.1 M NaNO ₃ aqueous solution, It relates to a method for producing a vinyl phosphate polymer comprising a step of mixing at a temperature of 30 ~ 70 ℃ by mixing a radical initiator, which is an azo compound having an amidine group or an azo compound having an imidazoline group, and a protic solvent.

Vinyl phosphate, polyvinyl phosphate, polymer electrolyte, azo compound, radical initiator, protic solvent

Description

Vinyl Phosphate Polymer and Method for Making the Same {POLY (VINYLPHOSPHONIC ACID) AND METHOD FOR PREPARING THE SAME}

The present invention relates to a vinyl phosphate polymer which is a polyelectrolyte and a preparation method thereof.

Vinyl phosphonic acid (poly (vinyl phosphonic acid)) is a polyelectrolyte (polyelectrolyte) has a phosphonic acid group (-PO ₃ H ₂ ) that can be ionized in the polymer chain shows ionic conductivity. In general, the properties of a polymer electrolyte are characterized by the degree of acidity or basicity of the functional groups on the polymer chain, the distance of the functional periods on the polymer chain, that is, the charge density of the polymer chain, the position of the functional groups in the polymer chain, and the counter ions of the polyions. ion).

Electrolyte interaction between ions occurs in the polymer electrolyte due to dissociation of ions in the polymer, which complicates the properties of the polymer electrolyte solution rather than the neutral polymer solution. In such a polymer electrolyte, a salt is added to the polymer aqueous solution to prevent gelation of the polymer electrolyte and its physical properties are measured.

The molecular weight of the polymer electrolyte is measured by light scattering in a salt solution of a predetermined concentration, and the molecular weight is obtained through a Zimmm Plot. The intrinsic viscosity of the polymer electrolyte is also a physical property that shows the relative molecular weight, and is measured under a salt solution of a predetermined concentration. Generally, an intrinsic viscosity is obtained by measuring the flow time of each polymer electrolyte using an Ubbelode viscometer.

A vinyl phosphate polymer is a polymer having a typical acidic group together with polyacrylic acid, polyvinyl sulfate or polystyrene sulfuric acid. It is a corrosion inhibitor, flame retardant, tooth material, fuel cell separator, dopant of conductive material, hydrogel for medicine delivery, and metal removal. It is applied to various fields such as filter material, high hygroscopic resin, dispersant, surface modifier and detergent additive.

In general, vinyl phosphate polymers are prepared through radical polymerization of vinyl phosphate monomers. Initially a polymerization process using peroxide or sulfate radical initiators of vinyl phosphate monomers in alcohol or aqueous solutions has been reported (German Patent 1,106,963). The polymerization yield was then increased by varying the amount of radical initiator and protic polymerization solvent of the peroxyester (US Pat. No. 4,696,987). However, both methods left residual monomer after polymerization and no polymer properties were reported.

The Wilson group then produced vinylphosphate polymers using azobisacrylonitrile initiators and applied them to dental materials (Journal of materials science letter 9, 1058-1060, 1990).

In Hynix Semiconductor, a vinyl phosphate polymer was prepared as an organic antireflective coating composition, and its molecular weight was as low as 4,530 (KR 564,430, US 7,198,887).

The molecular weight of the currently available commercially available vinyl phosphate polymer is approximately 24,000. Recently, the Wegner Group has produced a vinyl phosphate polymer with a molecular weight of 62,000 using a water-insoluble radical initiator and a dialyzed membrane to prepare the polymer. Separated. However, this method has a problem that it is difficult to apply commercially because mass polymerization is difficult and takes a long time. (Macromol. Rapid Commun 27, 1719, 2006).

In addition, the conventional vinyl phosphate polymer has a low molecular weight is broken after the film production or significantly lower durability, polymer production technology has a problem of separation process difficult to apply commercially.

Accordingly, an object of the present invention is to provide a high molecular weight vinyl phosphate polymer having excellent film properties and mechanical strength, and a method for producing the same, in order to solve the above technical problems.

The present invention to achieve the above object,

It provides a vinyl phosphate polymer having a weight average molecular weight of 100,000 ~ 500,000, having an intrinsic viscosity of 2 ~ 20 dl / g in 0.1M NaNO ₃ aqueous solution.

In addition, the present invention is a vinyl phosphate polymer comprising a step of mixing at a temperature of 30 ~ 70 ℃ by mixing a vinyl phosphate monomer, an azo compound having an amidine group or a radical initiator that is an azo compound having an imidazoline group, and a protic solvent It provides a method of manufacturing.

According to the present invention, a commercial process of a high molecular weight vinyl phosphate polymer is possible, and the prepared high molecular weight vinyl phosphate polymer has excellent film properties and mechanical strength, so that a membrane for a fuel cell, a dopant for a conductive material, and a hydrogel for pharmaceutical delivery Etc. can be used for various purposes.

Hereinafter, the present invention will be described in more detail.

The present invention is a polymer consisting of a vinyl phosphate monomer, having a weight average molecular weight of 100,000 to 500,000, a vinyl phosphate polymer and a vinyl phosphate monomer having an intrinsic viscosity of 2 to 20 dl / g in a 0.1 M NaNO ₃ aqueous solution, It relates to a method for producing a vinyl phosphate polymer comprising a step of mixing at a temperature of 30 ~ 70 ℃ by mixing a radical initiator, which is an azo compound having an amidine group or an azo compound having an imidazoline group, and a protic solvent.

The vinyl phosphate monomer may be represented by the following formula (1).

Azo compounds having the amidine group may be represented by the following formula (2).

In Chemical Formula 2,

R ¹ to R ⁵ are the same as or different from each other, hydrogen, substituted or unsubstituted C ₁ to C ₂₀ linear or branched alkyl, substituted or unsubstituted C ₃ to C ₂₀ cycloalkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, substituted or unsubstituted C ₇ -C ₁₄ arylalkyl, or substituted or unsubstituted C ₂ -C ₂₀ alkenyl,

R ¹ To When R ⁵ is substituted by a substituent, the substituent is one or more selected from -OH, -OR, -CO ₂ H, -CO ₂ R and -COR, wherein R is the same as or different from each other, C ₁ ~ C ₂₀ is alkyl.

The azo compound having an imidazoline group may be represented by the following Formula 3.

In Chemical Formula 3,

R ⁶ to R ⁸ are the same as or different from each other, hydrogen, substituted or unsubstituted C ₁ to C ₂₀ linear or branched alkyl, substituted or unsubstituted C ₃ to C ₂₀ cycloalkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, substituted or unsubstituted C ₇ -C ₁₄ arylalkyl, or substituted or unsubstituted C ₂ -C ₂₀ alkenyl,

R ⁶ To When R ⁸ is substituted by a substituent, the substituent is one or more selected from -OH, -OR, -CO ₂ H, -CO ₂ R and -COR, wherein R is the same as or different from each other, C ₁ ~ C ₂₀ is alkyl.

The vinyl phosphate monomer is a polar olefin having a phosphate group represented by Chemical Formula 1, and the vinyl phosphate polymer prepared according to the present invention is also a polymer of very high polarity, and its solubility varies depending on the solvent.

In particular, it is known that a phosphate group attached to a vinyl phosphate monomer or a vinyl phosphate polymer can form hydrogen bonds between monomers, within polymers, between polymers, or between monomers and polymers or form anhydride bonds through condensation reactions. (J. Am. Chem. Soc., 74, 3427, 1952).

This reaction is solvent dependent and has a very large influence on the solubility and polymerization of the polymer. The solubility characteristics of the monomers and polymers are not soluble in nonpolar solvents such as hexane and toluene, and the monomers are well soluble in polar solvents such as THF, acetone, alcohol and water, while the solubility of the polymer depends on the molecular weight of the polymer produced. And gelation occurs in some cases. On the other hand, since vinyl phosphate shows excellent polymerization characteristics with respect to a protic solvent such as water or alcohol, a protic solvent can be used as a polymerization solvent. Examples of protic solvents include water, methanol, ethanol, isopropanol, and the like. One kind selected from the group consisting of these may be used.

As the protic solvent (polymerization solvent), it is preferable to use 1% to 100% by weight of the vinyl phosphate monomer. Such a polymerization solvent may react with the monomer at the initial stage of the polymerization, or may be polymerized with dropwise addition of the polymerization solvent depending on the viscosity of the solution during the polymerization reaction. Bulk form polymerization can also be carried out without using this method.

Since the vinyl phosphate monomer, the resulting vinyl phosphate polymer and the protic solvent (polymer solvent) are all polar, the radical initiator should be well mixed with these polar conditions, have a low radical decomposition temperature and have a stable radical intermediate structure. A radical initiator having such conditions is an azo compound having an amidine group or an imidazoline group. An azo compound having an amidine group may be represented by Formula 2, and an azo compound having an imidazoline group may be represented by Formula 3.

Ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ) or potassium persulfate (K ₂ S ₂ O ₈ ), another radical initiator that is soluble in polar solvents, does not undergo polymerization and is azo-type azobisacryl Nitrile or azobiscyanobalaric acid also did not undergo polymerization. These results indicate that the radical initiator can be well mixed with the polar conditions and have a stable radical intermediate structure so that the polymerization can be performed.

Azo compounds having an amidine group or an imidazoline group can initiate polymerization at a low polymerization temperature of about 40 to 80 ° C., and can have a stable radical intermediate structure due to the resonance structure characteristics of the amidine group or the imidazole group.

Examples of such radical initiators include 2,2'-azobis (2-methylpropionamidine), 2,2'-azobis (N-butyl-2-methylpropionamidine), 2,2'-azobis (N-cyclohexyl-2-methylpropionamidine), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamidine], 2,2'-azobis [N- ( 2-carboxyethyl) -2-methylpropionamidine], 2,2'-azobis [2-methyl-N- (2-hydroxybutyl] propionamidine, 2,2'-azobis {2- Methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamidine}, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] , 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, etc. The salt compounds or hydrates of these halides May be used.

The amount of the radical initiator used is preferably 0.01 to 1% relative to the molar amount of the vinyl phosphate monomer. Such radical initiators may be polymerized with the monomers at the beginning of the polymerization or with a small dropwise addition during the polymerization reaction.

It is preferable that a polymerization temperature range is 30-70 degreeC, and a polymerization temperature can change during reaction and change polymerization conditions. If the polymerization temperature exceeds 70 ℃, the molecular weight of the vinyl phosphate polymer is lowered, if less than 30 ℃ polymerization reaction does not occur smoothly.

The polymerization method according to the present invention can be polymerized by mixing a vinyl phosphate monomer and a radical initiator in a protic solvent, and controlling the polymerization yield and molecular weight through the construction and quantification of the radical initiator and the polymerization solvent.

The vinyl phosphate polymer in the polymerization solution has a strong interaction with the residual monomer in the polymer during the polymer recovery process due to strong interaction between the polymer by the phosphate group, or between the polymer and the residual monomer. Therefore, the related art related to vinyl phosphate polymer recovery has been left for a long time through the dialysis membrane to remove the residual monomer and low molecular weight polymer to recover the desired polymer. In this case, it is difficult to apply to the mass polymerization, it takes a long time and it is not effective and it is difficult to apply commercially.

Polymer recovery process of the present invention is as follows. First, after polymerization, the polymerization solution having a high viscosity is appropriately diluted with distilled water, and then the diluted polymerization solution is added dropwise to the non-solvent. At this time, the non-solvent can be precipitated while preventing the aggregation of the vinyl phosphate polymer by stirring using a strong homogenizer (homogenizer).

At this time, the solvent selection is important, but the particles of the precipitated polymer are uniformly mixed with the residual monomers, and it must be able to prevent the aggregation of the precipitated polymer. As such a solvent, alcohols such as methanol, ethanol, propanol and butanol, or polar solvents such as acetone and THF are preferable, and THF is most effective.

The manufacturing method of the vinyl phosphate polymer including the polymer recovery step is a commercial process is possible because the precipitated particles are stably present without agglomeration with each other.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments of the present invention may be modified in various forms, the scope of the present invention is not limited to the embodiments described below.

Example 1 Vinyl Phosphoric Acid Polymer Preparation

Vinyl phosphoric acid (2 g, 18.5 mmol) and 2,2'-azobis (2-methylpropionamidine) dihydrochloride (5.02 mg, 18.5x10 ^-3 mmol) were added to a 100 ml Schlenk flask and milliqui ( mili-Q) 1g of purified water was dissolved. After vacuum / argon purging three times, the reaction was carried out at 70 ° C. The viscosity increased as bubbles were formed in the reaction solution during the reaction. After reacting for 18 hours, distilled water (5 ml) was added thereto, and the diluted polymer solution was slowly added dropwise to agitated THF (200 ml) using a homogenizer to prevent the precipitated polymer from agglomeration. This process was repeated twice, and the precipitate was filtered through a paper filter, and the recovered polymer was dried at 60 ° C. for 24 hours in a vacuum oven to obtain 1.1 g of vinyl phosphate polymer (55 wt% based on the total amount of monomer injected).

Example 2 Vinyl Phosphoric Acid Polymer Preparation

Under the same polymerization conditions as in Example 1, the polymerization was carried out for 18 hours at a polymerization temperature of 60 ℃. The polymerization reaction and the polymer recovery process were carried out in the same manner as in Example 1 to obtain 1.4 g of vinyl phosphate polymer (68% by weight based on the total amount of added monomers).

<Example 3> Preparation of vinyl phosphate polymer by dropwise addition of additional polymerization solvent

Vinyl phosphate (15 g, 138.85 mmol) and 2,2'-azobis (2-methylpropionamidine) dihydrochloride (37.7 mg, 138.85x10 ^-3 mmol) were added to a 250 ml Schlenk flask and milliqui distilled water ( 1 g) was dissolved. After vacuum / argon purging three times, the reaction was carried out at 60 ° C. After the reaction for 1 hour, distilled water (0.5 g) was added dropwise when the viscosity increased as bubbles were generated in the reaction solution. Thereafter, 1 g of distilled water was added dropwise for 7 hours every 1 hour. After reacting for 10 hours and diluting with distilled water (30ml), the diluted polymer solution was slowly added dropwise to THF (1L) with vigorous stirring using a homogenizer to prevent the precipitated polymer from agglomeration. This process was repeated twice, and the precipitate was filtered through a paper filter, and the recovered polymer was dried in a vacuum oven at 60 ° C. for 24 hours to obtain 11.5 g of vinyl phosphate polymer (76 wt% based on the total amount of monomer introduced).

Example 4 Vinyl Phosphate Polymer Preparation

100 ml Schlenk with vinyl phosphate (2 g, 18.5 mmol) and 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (6.00 mg, 18.5x10 ^-3 mmol) Into the flask was dissolved 1g of milliquin purified water. The reaction was carried out at 70 ° C. after three vacuum / argon purging cycles. The viscosity increased as bubbles were formed in the reaction solution during the reaction. After reacting for 18 hours, distilled water (5 mL) was added thereto, and the diluted polymer solution was slowly added dropwise to THF (200 mL) with vigorous stirring using a homogenizer to prevent clumping of the precipitated polymer. This process was repeated twice, and the precipitate was filtered through a paper filter, and the recovered polymer was dried in a vacuum oven at 60 ° C. for 24 hours to obtain 1.2 g of vinyl phosphate polymer (60 wt% based on the total amount of monomer injected).

Example 5 Vinyl Phosphoric Acid Polymer Preparation

Under the same polymerization conditions as in Example 4, the polymerization was carried out at 60 ° C polymerization temperature for 18 hours. Polymerization and polymer recovery were carried out in the same manner as in Example 1 to obtain 1.1 g of vinyl phosphate polymer (55 wt% based on the total amount of monomers introduced).

<Example 6> Preparation of vinyl phosphate polymer by dropwise addition of a polymerization solvent

250 ml Schlenk flask with vinyl phosphate (20 g, 185.13 mmol) and 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (60 mg, 185.13x10 ^-3 mmol) Add distilled water (2 g) and dissolve it. The reaction was carried out at 50 ° C. after three vacuum / argon purging. After the reaction for 2 hours, distilled water (1.0 g) was added dropwise when the viscosity increased as bubbles were generated in the reaction solution. After 1 hour 2g of distilled water was added dropwise for 3 hours. After reacting for 18 hours, distilled water (70 ml) was added thereto and diluted. The diluted polymerization solution was slowly added dropwise to THF (1 L) with vigorous stirring using a homogenizer to prevent clumping of the precipitated polymer. This process was repeated twice, and the precipitate was filtered through a paper filter, and the recovered polymer was dried in a vacuum oven at 60 ° C. for 24 hours to obtain 7.8 g of vinyl phosphate polymer (39 wt% based on the total amount of monomer injected).

Comparative Example 1 Trial of Production of Vinyl Phosphate Polymer by Potassium Persulfate Radical Initiator

Vinyl phosphate (2 g, 18.5 mmol) and potassium persulfate (12.5 mg, 46.25x10 ^-3 mmol) were added to a 100 ml Schlenk flask and dissolved in 1 g of milliquique purified water. The reaction was carried out at 60 ^° C. after three vacuum / argon purging. After reacting for 24 hours, the polymerization solution was added dropwise to insoluble solvent THF (200 mL), but no polymer precipitate formed.

Comparative Example 2 Attempt to Prepare Vinyl Phosphate Polymer by Ammonium Persulfate Radical Initiator

Vinyl phosphate (2 g, 18.5 mmol) and ammonium persulfate (10.55 mg, 46.25x10 ^-3 mmol) were added to a 100 ml Schlenk flask and dissolved in 1 g of milliquique purified water. After vacuum / argon purging three times, the reaction was carried out at 60 ° C. After the reaction for 24 hours, the polymerization solution was added dropwise to THF (200 mL), which is a non-solvent, but no polymer precipitate was formed.

Comparative Example 3 Attempt to Prepare Vinyl Phosphate Polymer by 4,4'-Azobis (4-Cyanobalic Acid) Radical Initiator

Vinyl phosphate (2g, 18.5mmol) and 4,4'-azobis (4-cyanobalic acid) (12.96mg, 46.25x10 ^-3 mmol) were added to a 100ml Schlenk flask and 1g of Milliqui purified water. Melted. After vacuum / argon purging three times, the reaction was carried out at 60 ° C. After reacting for 24 hours, the polymerization solution was added dropwise to insoluble solvent THF (200 mL), but no polymer precipitate formed.

Comparative Example 4 Preparation of Vinyl Phosphate Polymer by AIBN Radical Initiator

Vinyl phosphoric acid (2 g, 18.5 mmol) and AIBN (60 mg) were added to a 100 ml Schlenk flask and 1 g of ethyl acetate was dissolved. After vacuum / argon purging three times, the reaction was carried out at 80 ° C. After reacting for 24 hours, the polymerization solution was diluted with distilled water and precipitated in acetone, which is an insolvent. The precipitate was dissolved in water again and precipitated in acetone solvent twice, followed by drying under vacuum oven at 60 ° C. for 24 hours. The yield was 1.8 g (90%) and the weight average molecular weight was about 5200.

As can be seen from Comparative Examples 1 to 3, the three radical initiators described above, namely potassium persulfate, ammonium persulfate, and 4,4'-azobis (4-cyanobalaric acid), are representatively soluble in aqueous solution. Although it was a radical initiator, it showed no polymerization reaction because it was an unstable radical initiator structure which cannot polymerize a vinyl phosphate monomer. On the other hand, the AIBN initiator, which is not water soluble and soluble in an organic solvent (Comparative Example 4), was well polymerized under a polar solvent such as ethyl acetate, but had a very low molecular weight of 5200. This is because the vinyl phosphate polymer produced during polymerization has low solubility in polar organic solvents, making it difficult to produce high molecular weight polymers.

Comparative Example 5 Preparation of Vinyl Phosphate Polymer at 80 ° C Polymerization Temperature

Under the same polymerization conditions as in Example 1, the polymerization was carried out at 80 ℃ polymerization temperature for 5 hours. The polymerization reaction and the polymer recovery process were carried out in the same manner as in Example 1 to obtain 1.5 g of vinyl phosphate polymer (75 wt% based on the total amount of monomer introduced).

<Viscosity measurement>

Viscosity measurements were performed on the polymers of Comparative Examples 5, 4, 5, and 6 prepared at polymerization temperatures of 80 ° C, 70 ° C, 60 ° C, and 50 ° C, respectively. Viscosity measuring equipment uses a Ubbelode viscometer and the flow time at room temperature was 90.08 seconds. As solvent, 0.1 M NaNO ₃ solvent was used, and the polymer concentration of 0.1 M NaNO ₃ solvent was changed for each polymer to measure the flow time, and the relative viscosity was linearized to obtain the intercept, thereby obtaining the intrinsic viscosity ( intrinsic viscosity). The viscosity measurement results are shown in Table 1.

division Comparative Example 5 Example 4 Example 5 Example 6 Polymerization temperature (℃) 80 70 60 50 Intrinsic Viscosity (dl / g) 1.62 2.54 3.15 4.64

As shown in Table 1, it can be seen that the intrinsic viscosity of the polymer increases as the polymerization temperature decreases. This indicates that the molecular weight increases as the polymerization temperature decreases.

<Measurement of molecular weight by dynamic light scattering>

Molecular weight measurement by dynamic light scattering was performed on the polymers of Comparative Examples 5, 5 and 6 prepared at polymerization temperatures of 80 ° C, 60 ° C and 50 ° C, respectively. The measuring instrument was an ALV-5000 instrument with He-Ne laser at 633 nm and 20 mW. The polymer solution was purified through a dialysis membrane using a 10 g / L NaH ₂ PO ₄ standard solvent and prepared at a concentration ranging from 0.2 to 8.0 g / l. All samples were measured through a cylinder sample cell at room temperature, and the Zimmm Plot was calculated for the scattering angle with respect to the concentration, and the molecular weight was obtained therefrom. In addition, the refractive index change rate (dn / dc) with respect to the concentration change was measured by Scanning Michelson Interferometer at the same wavelength using a 10g / L NaH ₂ PO ₄ standard solvent. 2 and 3 show the Zimmm Plot for each polymer. Table 2 shows refractive index change rate (dn / dc) and molecular weight (Mw).

division Comparative Example 5 Example 5 Example 6 Polymerization temperature (℃) 80 60 50 dn / dc (ml / g) 0.233 0.1286 0.1224 Mw 47,600 125,000 187,000

As a result of measuring the molecular weight by the dynamic light scattering method, the polymer produced at the polymerization temperature of 50 ℃ and 60 ℃ showed a molecular weight of 100,000 or more.

1 is a diagram showing a ¹ H NMR spectrum of a vinyl phosphate polymer.

FIG. 2 is a diagram showing a ZIMM PLOT by a dynamic light scattering method for a vinyl phosphate polymer prepared at a polymerization temperature of 50 ° C. FIG.

FIG. 3 is a diagram showing a ZIMM PLOT by a dynamic light scattering method for a vinyl phosphate polymer prepared at a polymerization temperature of 60 ° C. FIG.

Claims (11)

delete A vinyl phosphate monomer represented by Formula 1 below; A radical initiator having an azo compound having an amidine group represented by the following formula (2) or an azo compound having an imidazoline group represented by the following formula (3); And mixing the protic solvent and polymerizing at a temperature of 30 to 70 ° C. [Formula 1]

[Formula 2]

In Chemical Formula 2, R ¹ to R ⁵ are the same as or different from each other, hydrogen, substituted or unsubstituted C ₁ to C ₂₀ linear or branched alkyl, substituted or unsubstituted C ₃ to C ₂₀ cycloalkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, substituted or unsubstituted C ₇ -C ₁₄ arylalkyl, or substituted or unsubstituted C ₂ -C ₂₀ alkenyl; R ¹ to When R ⁵ is substituted by a substituent, the substituent is one or more selected from -OH, -OR, -CO ₂ H, -CO ₂ R and -COR, wherein R is the same as or different from each other, C ₁ ~ C ₂₀ is alkyl: (3)

In Chemical Formula 3, R ⁶ to R ⁸ are the same as or different from each other, hydrogen, substituted or unsubstituted C ₁ to C ₂₀ linear or branched alkyl, substituted or unsubstituted C ₃ to C ₂₀ cycloalkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, substituted or unsubstituted C ₇ -C ₁₄ arylalkyl, or substituted or unsubstituted C ₂ -C ₂₀ alkenyl; R ⁶ to When R ⁸ is substituted by a substituent, the substituent is one or more selected from -OH, -OR, -CO ₂ H, -CO ₂ R and -COR, wherein R is the same as or different from each other, C ₁ ~ C ₂₀ is alkyl. delete delete The method according to claim 2, wherein the protic solvent is 1 to 100% of the total weight of the vinyl phosphate monomer using a method of producing a vinyl phosphate polymer. The method of claim 2, wherein the protic solvent is at least one selected from the group consisting of water, methanol, ethanol, and isopropanol. The method of claim 2, wherein the radical initiator uses 0.01 to 1% relative to the mole of vinyl phosphate monomer. The method of claim 2, wherein the radical initiator is 2,2'-azobis (2-methylpropionamidine), 2,2'-azobis (N-butyl-2-methylpropionamidine), 2,2'- Azobis (N-cyclohexyl-2-methylpropionamidine), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamidine], 2,2'-azobis [N -(2-carboxyethyl) -2-methylpropionamidine], 2,2'-azobis [2-methyl-N- (2-hydroxybutyl] propionamidine, 2,2'-azobis { 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamidine}, 2,2'-azobis [2- (2-imidazolin-2-yl) Propane], 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} and their salt compounds or hydrates with halides Method for producing a vinyl phosphate polymer is one or more selected from. The method of claim 2, further comprising diluting the polymerization solution obtained after the polymerization step with distilled water, and then precipitating and recovering the polymer by dropwise adding the diluted polymerization solution to an insoluble solvent. . The method of claim 9, wherein the insolvent is methanol, ethanol, propanol, butanol, acetone or THF. The method for producing a vinyl phosphate polymer according to claim 9, wherein the insoluble solvent is stirred.

Images