KR102123279B1 - Method for separating partial (meth)acrylated polyols and urethane-based materials functionalized with (meth)acrylate produced by the partial (meth)acrylated polyols - Google Patents

Abstract

The separation method of the partial (meth)acrylated polyol of the present invention comprises the steps of reacting a triol and (meth)acrylate; Primary extraction by adding water to the partial (meth)acrylated polyol prepared from the reacting step; And in the first extraction step, a first organic phase and a first aqueous phase are separated, and a second extraction is performed by adding a solvent to the aqueous phase.
The urethane-based material functionalized with (meth)acrylate of the present invention can be prepared by reaction with a partial (meth)acrylated polyol and isocyanate.

Description

Method for separating partial (meth)acrylated polyol and functionalized urethane-based material functionalized with (meth)acrylate prepared therefrom (meth)acrylated polyols and urethane-based materials functionalized with (meth) acrylate produced by the partial (meth)acrylated polyols}

Various embodiments of the present invention is a method for producing mono-(meth)acrylated polyols and di-(meth)acrylated polyols and separation thereof How to do. More specifically, trivalent alcohols (e.g. trimethylolpropane, trimethylolethane and trimethylolryhane) and photo-curable trivalent from (meth)acrylate It relates to a method for producing mono- and di- (meth) acrylate and a method for separating it. In addition, the present invention relates to photo-curable poly-, multi- and diurethanes made from trivalent mono- and di-(meth)acrylates and di- or polyisocyanates. In addition, the present invention provides these urethane-based materials for different applications of photo-curable poly-, multi- and diurethanes, such as plastics, crosslinkers, resins, coatings, and (3D)-printing by photo-induced polymerization. It relates to the use of.

(Meth)acrylate, a photo-curable unsaturated monomeric material, has been used for a wide range of applications. Existing (meth)acrylate homopolymerization was easily carried out through a glass-radical chaining process using a photo-initiator by photo-radiations. Today, UV-curable polyurethane acrylates and acrylic resins are available in a variety of markets. Among them, polyol-based acrylic resins as high active diluents are widely used in various applications due to their useful properties, such as rapid treatment, improved coating mechanical properties and high stiffness.

Polyol-based acrylic resins such as trimethylolpropane acrylate, pentaerythritol acrylate and neopentyl glycol acrylate were synthesized and the properties of the cured acrylate were studied. However, these polyol-based (meth)acrylates are mixtures of mono-, di- and multi-(meth)acrylated polyols or fully (meth)acrylated polyols (e.g. trimethylolpropane tri(meth)acrylate) And pentaerythritol tetra(meth)acrylate).

In the case of trihydric alcohols, trimethylolpropane, 1,1,1-trimethylolpropane triacrylate and trimethacrylate are the only commercially available bulk chemical markets. Accordingly, there is a need for an efficient method and separation of trimethylolpropane mono-(meth)acrylate and di-(meth)acrylate. Highly reactive (meth)acrylate groups can be readily polymerized at high temperatures, for example, during distillation for separation of these components from the reaction mixture. Alternatively, fully (meth)acrylated polyols were prepared to avoid complex separation of partially (meth)acrylated polyols by using excess (meth)acrylate in the polyol. Additionally, chromatographic methods cannot be applied to large-scale production of industrial bulk chemicals.

1: Representative polyols, such as trimethylolpropane, trimethylolethane, pentaerythritol

2: (meth)acrylate

3: mono-(meth)acrylated polyols

4: di-(meth)acrylated polyols

5: tri-(meth)acrylated polyols

6: Tetra-(meth)acrylated polyols.

In the prior art, there have been many reports regarding the preparation of mixtures of multi-(meth)acrylated polyols as useful acid-catalyzed (meth)acrylates. For example, 250 ml of ditrimethylolpropane (25 g, 0.2 mol), acrylic acid (7.3 ml, 0.46 mol), p-toluenesulfonic acid (4.3 g), benzene (40 g), and hydroquinone (0.25 g) Mix in a glass flask, slowly heat up to 82° C., and react for 8 hours. After the separation process, a pale liquid of a ditrimethylolpropane acrylate mixture was obtained (yield: 63.5%), and ditrimethylolpropane acrylate was subjected to UV-curing tests with a higher cure rate than that of trimethylolpropane triacrylate. Applied.

As another example, pentaerythritol (3mole, 409g) is a cuprous oxide (3g, polymerization inhibitor) and p-methoxyphenol (1%, inhibitor) in anhydrous benzene at about 88°C with 46g concentrated sulfuric acid as catalyst. And reacted with excess (18 mole, 1296 g) glacial acrylic acid. After the separation process, 316 g per mole of pentaerythritol used was obtained as a mixture of tri- and tetra-acrylated pentaerythritol with a molar ratio of 0.54:0.46. However, in these examples, only a mixture of polyol acrylates was prepared.

On the other hand, these partial (meth)acrylated polyols, for example, mono- and di-(meth)acrylated trimethylolpropane, mono- and di-(meth)acrylated trimethylolethane, mono-, di -And tri-(meth)acrylated pentaerythritol are also useful and important as multi-functional reactive monomers with photo-curable groups and hydroxyl groups in the molecule. Accordingly, the hydroxyl groups of these functional monomers react with isocyanates such as toluene diisocyanate (TDI) and methylenediphenyl diisocyanate (TDI), and hexamethylene diisocyanate (HDI) to (meth)acrylate Chemical-polyurethanes or urethane compounds can be formed, which in turn can be further polymerized by light-irradiation. The materials and polymerization process can be used in different applications, for example, the use of the urethane-based polymers for coatings and (3D)-printing.

Recently, we have found a possible and simple method for the preparation and separation of partially (meth)acrylated polyols, which can be used as multi-functional reactive monomers.

The present invention provides an easy manufacturing process of mono- and di-(meth)acrylated trimethylolpropane, and mono- and di-(meth)acrylated trimethylolethane, respectively. The separation process involves several steps of liquid-liquid extraction using water and an organic solvent to extract the residual polyol, mono-(meth)acrylated polyol, and di-(meth)acrylated polyol, respectively, from their reaction solution. Is made of Moreover, a process for the preparation of (meth)acrylated polyurethanes from (meth)acrylated polyols having hydroxyl groups by reaction with diisocyanates has been developed. In addition, a process for the preparation of (meth)acrylated polyurethanes from (meth)acrylated polyols having at least two hydroxyl groups by reaction with di- or poly-isocyanates has been developed. In addition, a method for producing (meth)acrylated polyurethanes from (meth)acrylated polyols having hydroxyl groups by reaction with poly-isocyanates has been developed. In addition, methods have been developed for use in the use of the urethane-based polymers for different applications, for example coatings and (3D)-printing.

The separation method of the partial (meth)acrylated polyol of the present invention comprises the steps of reacting a triol and (meth)acrylate; Primary extraction by adding water to the partial (meth)acrylated polyol prepared from the reacting step; And in the first extraction step, a first organic phase and a first aqueous phase are separated, and a second extraction is performed by adding a solvent to the aqueous phase.

The urethane-based material functionalized with (meth)acrylate of the present invention can be prepared by reaction with a partial (meth)acrylated polyol and isocyanate.

The present invention allows the production and separation of partially (meth)acrylated polyols, which can be used as multi-functional reactive monomers, by simple methods. In addition, a urethane-based material functionalized with (meth)acrylate may be prepared using a partially (meth)acrylated polyol prepared and separated therefrom. In addition, urethane-based materials functionalized with (meth)acrylates can be used in various fields.

1 is a schematic diagram of a method for separating a partial (meth)acrylated polyol of the present invention.
Figure 2 (A) is a GC chromatogram of reactants of trimethylolpropane and methacrylic acid at 80 °C for 15 hours.
2B is a GC chromatogram for the first organic phase in the primary extraction.
2(C) is a GC chromatogram for the first aqueous phase in the primary extraction.
Figure 2 (D) is a GC chromatogram for the second aqueous phase in the secondary extraction.
2(E) is a GC chromatogram for the second organic phase in the secondary extraction.
2(F) is a GC chromatogram of mono-methacrylated trimethylolpropane from the second organic phase.
FIG. 2G is a GC chromatogram of di-methacrylated trimethylolpropane from the first organic phase.
3(A) is an FT-IR spectra of di-methacrylated trimethylolpropane.
Fig. 3B is the FT-IR spectra of toluene 2,4-diisocyanate.
Figure 3 (C) is the FT-IR spectra of the reaction component and the diurethane product formed after 1 hour of reaction of di-methacrylated trimethylolpropane and toluene 2,4-diisocyanate at 80 °C.
4(A) is the FT-IR spectra of mono-methacrylated trimethylolpropane.
Fig. 4B is the FT-IR spectra of toluene 2,4-diisocyanate.
Figure 4 (C) is the FT-IR spectra of the polyurethane product formed after 1 hour of reaction of the reaction component and mono-methacrylated trimethylolpropane and toluene 2,4-diisocyanate at 80 °C.

Hereinafter, various embodiments of the present document will be described with reference to the accompanying drawings. It should be understood that the examples and terms used therein are not intended to limit the technology described in this document to specific embodiments, but include various modifications, equivalents, and/or substitutes of the examples.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The present invention relates to a simple method for the production and separation of partially (meth)acrylated polyols, which can be used as multi-functional reactive monomers.

The invention provides the preparation of UV-curable mono- and di-(meth)acrylate polyols from polyols and (meth)acrylates, and their UV-curable poly- and oligo-urethanes, useful as monomers and crosslinkers in polymer production It's about how. Moreover, the present invention relates to the use of the urethane-based polymers for different applications, for example coatings and (3D)-printing.

The invention is partially (meth)acrylated from the reaction of polyols and (meth)acrylates in the presence of acidic catalysts and inhibitors in solution and in any organic solvent at a temperature of 20 to 150°C, preferably 50 to 100°C. High-selectivity manufacturing processes for polyols, such as mono-trimethylolpropane and di-trimethylolpropane. Preferred solvents can be water-immiscible solvents, for example benzene, toluene, xylene, ethyl acetate, ether, and higher-carbon alcohols or mixtures thereof or mixtures containing these solvents. Depending on the conditions, only minor traces of unwanted by-products, tri-methacrylated triols, can be formed.

The present invention also relates to a method of extracting the residual polyol, mono-(meth)acrylated polyol, and di-(meth)acrylated polyol, respectively, from their reaction solution. Primary extraction by adding water to the previously prepared partial (meth)acrylated polyol; And in the first extraction step, a first organic phase and a first aqueous phase are separated, and a second extraction is performed by adding a solvent to the aqueous phase. After the first extraction, the step of obtaining a di-(meth)acrylated polyol from the first organic phase may be further included. In the second extraction step, the second organic phase and the second aqueous phase are separated, and may further include the step of obtaining a mono-(meth)acrylated polyol from the second organic phase.

That is, by including several steps of liquid-liquid extraction using water and an organic solvent, (meth)acrylated polyols generated from the reaction solution, such as mono-trimethylolpropane and di-trimethylolpropane are separated. can do. Preferred solvents, any solvents which are immiscible with water to form two phases, are benzene, toluene, xylene, ethyl acetate, dichloromethane, chloroform, ether, and higher alcohols, or mixtures thereof or mixtures containing these solvents. Can be.

In addition, the present invention is hydroxyl by reaction with an aliphatic, alicyclic, aromatic or aromatic-aliphatic diisocyanate under solvent and solventless conditions at a temperature of 10 to 200 ^o C, preferably 30 to 100 ^o C. It relates to a process for producing a (meth)acrylated urethane from a (meth)acrylated polyol having a group.

At this time, preferred diisocyanates are toluene diisocyanate (TDI), methylenediphenyl diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate, pentamethylene diisocyanate, tetramethylene diisocyanate, or xylylene diisocyanate. It may be an isocyanate or a mixture thereof or a mixture containing the polyisocyanate, diisocyanate and isocyanate.

The present invention also provides hydroxyl groups by reaction with aliphatic, cycloaliphatic, aromatic or aromatic-aliphatic poly-isocyanates under solvent and solvent-free conditions at a temperature of 10-200 ^o C, preferably 30-100 ^o C. It relates to a process for producing a (meth)acrylated multi-urethane from a (meth)acrylated polyol having. Preferred poly-isocyanates can be Basonat ^® and Desmodur ^® , or mixtures thereof or mixtures containing the polyisocyanates, diisocyanates and isocyanates.

In addition, the present invention is at least 2 by reaction with an aliphatic, alicyclic, aromatic or aromatic-aliphatic diisocyanate or polyisocyanate under solvent and solvent-free conditions at a temperature of 10-200 ^o C, preferably 30-100 ^o C. It relates to a process for preparing a (meth)acrylated polyurethane from a (meth)acrylated polyol having two hydroxyl groups. Preferred di- and poly-isocyanates are toluene diisocyanate (TDI), methylenediphenyl diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate, pentamethylene diisocyanate, tetramethylene diisocyanate, xylylene Diisocyanate, Basonat ^® or Desmodur ^® , or a mixture thereof or a mixture containing the polyisocyanate, diisocyanate and isocyanate.

The invention also relates to methods for use in the use of the urethane-based polymers for different applications, for example plastics, crosslinkers, resins, coatings, and (3D)-printing by photo-induced polymerization. The (meth)acrylated-diurethane and polyurethane can be polymerized with any initiator under solvent and solvent-free conditions by a photo-induced process at a temperature of 10-200 ^o C, preferably 30-100 ^o C. have.

It will be described in more detail below.

1. Preparation of high selectivity of partially (meth)acrylated polyols

The present invention relates to a high selectivity manufacturing process of partially (meth)acrylated polyols from the reaction of polyols and (meth)acrylates. At this time, the polyol and (meth)acrylate may be reacted at a temperature of 20 to 150°C, preferably 50 to 100°C, in the presence of a solution and any organic solvent, acid catalyst and inhibitor. Partial (meth)acrylated polyols such as mono-trimethylolpropane and di-trimethylolpropane can be prepared and separated from this reaction.

Specifically, triol (e.g., trimethylolpropane or trimethylolethane) may be used in the presence of a solution (meth) ) It can react with acrylate. In this case, the triol and (meth)acrylate are in a ratio of 1:5 (mole/mole), preferably in a ratio of 1:2 (mole/mole), preferably in a ratio of 1:1 (mole/mole), Preferably it can react at a ratio of 1:0.5 (mole/mole). The (meth)acrylate may be (meth)acrylic acid or (meth)acrylic acid alkyl ester.

In this case, the solvent may be a water-immiscible solvent, for example, benzene, toluene, xylene, ethyl acetate, ether, and higher-carbon alcohols or a mixture thereof or a mixture containing the solvents.

Preferred acidic catalysts are hydrofluoric acid, sulfuric acid, phosphoric acid, aluminum trichloride, toluenesulfonic acid, niobic acid, polystyrene sulfonate, heteropoly acid, acidic cation-exchange resin and zeolite. However, the type of catalyst used is not limited. The catalyst may preferably be used in a ratio of 0.01 to 100% with respect to the polyol. The inhibitor may be hydroquinone, cuprous oxide and p-methoxyphenol, or mixtures thereof or mixtures containing the inhibitors. The organic solvent can be selected from DMF, DMSO, pyridine, hydrocarbon and cyclic hydrocarbon, alkyl ester, alcohol, ketone and mixtures thereof, but is not limited to the reaction. Preferred solvents are water-immiscible solvents, for example benzene, toluene, xylene, ethyl acetate, ether, and higher alcohols or mixtures thereof, or mixtures containing these solvents. The organic solvent may be used in a ratio of preferably 1 to 3000%, preferably 50 to 1000% with respect to the polyol. Under these conditions, only minor traces of unwanted byproducts, tri-methacrylated triols, such as tri-(meth)acrylated trimethylolpropane, can be formed.

<Scheme 1>

1: Triol (e.g. trimethylolpropane and trimethylolpropane)

2: (meth)acrylate

3: mono-(meth)acrylated triol

4: di-(meth)acrylated triol

5: Tri-(meth)acrylated triol

2. Separation of partially (meth)acrylated polyol from reaction solution

The present invention is a method for extracting the residual polyol, mono-(meth)acrylated polyol, and di-(meth)acrylated polyol, respectively, from the previous reaction solution. The present invention includes (meth)acrylated polyols generated from reaction solutions, such as mono-trimethylolpropane and di-trimethylolpropane, by including several steps of liquid-liquid extraction using water and organic solvents. It relates to the separation process. Preferred solvents are benzene, toluene, xylene, ethyl acetate, dichloromethane, chloroform, ether, and higher alcohols, or mixtures of these solvents or mixtures of these solvents, with any solvent immiscible with water making the two phases .

Specifically, referring to FIG. 1, as a primary extraction step, after the reaction is completed, water is added to the reactants to form two phases of the aqueous and organic phases, and the aqueous phase is extracted. Water may preferably be used in a ratio of 5 to 500% with respect to the polyol, preferably in a ratio of 10 to 100%, preferably in a ratio of 20 to 50%. This extraction is repeated multiple times, preferably 5 to 15 times, but is not limited.

As a secondary extraction step, the aqueous phase is pooled and a water-immiscible solvent is added to the aqueous solution to make the secondary two phases of the aqueous and organic phases, and the aqueous phase is extracted. Preferred solvents, any solvent that is immiscible with water to make two phases are benzene, toluene, xylene, ethyl acetate, dichloromethane, chloroform, ether, and higher alcohols, or mixtures thereof or mixtures containing these solvents to be. The solvent may preferably be used in a ratio of 5 to 500% with respect to the aqueous solution, preferably in a ratio of 10 to 100%, preferably in a ratio of 20 to 50%. This extraction is repeated multiple times, preferably 2 to 5 times, but is not limited. After the organic phase is pooled and dried using molecular sieves, mono-(meth)acrylated polyols can be obtained by simple evaporation of the solvent.

On the other hand, after drying the organic phase from the primary extraction step with a molecular sieve, a di-(meth)acrylated polyol can be obtained by simple evaporation of the solvent.

3. Preparation of (meth)acrylated diurethane

The production of the (meth)acrylated diurethane can be carried out by reaction of a (meth)acrylated polyol having a hydroxyl group with diisocyanate.

<Reaction Scheme 2> Example of (meth)acrylated diurethane formation from di-(meth)acrylated trimethylolpropane and diisocyanate

Partial (meth)acrylated polyols with hydroxyl groups have a ratio in the range of 0.1:1-50:1 (mole/mole) under solvent or solvent-free conditions at a temperature of 20-150°C, preferably 50-100°C. , Preferably in a ratio ranging from 0.5:1 to 10:1 (mole/mole), preferably in a ratio ranging from 1:1 to 5:1 (mole/mole), preferably 1:1-2:1 ( mole/mole) ratio, it can be reacted with an aliphatic, alicyclic, aromatic or aromatic-aliphatic diisocyanate. However, the ratio of the (meth)acrylated polyol and diisocyanate is not limited in the reaction. The organic solvent can be selected from DMF, DMSO, pyridine, hydrocarbon and cyclic hydrocarbon, alkyl ester, alcohol, ketone and mixtures thereof, but is not limited to the reaction. The organic solvent may preferably be used in a ratio of 1 to 3000%, preferably 50 to 1000%, relative to the (meth)acrylated polyol.

4. Preparation of (meth)acrylated multi-urethane

The production of the (meth)acrylated multi-urethane can be carried out by the reaction of a (meth)acrylated polyol having hydroxyl groups with a poly-isocyanate.

<Reaction Scheme 3> Example of (meth)acrylated multi-urethane production from di-(meth)acrylated trimethylolpropane and polyisocyanate (triisocyanate).

Partial (meth)acrylated polyols with hydroxyl groups have a ratio in the range of 0.1:1-100:1 (mole/mole) under solvent or solvent-free conditions at a temperature of 20-150°C, preferably 50-100°C. , Preferably in the range of 0.5:1-50:1 (mole/mole), preferably in the range of 1:1-10:1 (mole/mole), preferably in the range 1:1-3:1 ( mole/mole) in a ratio in the range of aliphatic, alicyclic, aromatic or aromatic-aliphatic tri- and poly-isocyanates. However, the ratio of (meth)acrylated polyol and tri- and poly-isocyanate is not limited in the reaction. The organic solvent can be selected from DMF, DMSO, pyridine, hydrocarbon and cyclic hydrocarbon, alkyl ester, alcohol, ketone and mixtures thereof, but is not limited to the reaction. The organic solvent may preferably be used in a ratio of 1 to 3000%, preferably 50 to 1000%, relative to the (meth)acrylated polyol.

5. Preparation of (meth)acrylated polyurethane

The production of (meth)acrylated polyurethane can be carried out by reaction of a (meth)acrylated polyol having at least two hydroxyl groups with di- or poly-isocyanate.

<Reaction Scheme 4> Example of the production of (meth)acrylated polyurethane from mono-(meth)acrylated trimethylolpropane and di- or poly-isocyanate.

Partial (meth)acrylated polyols having at least two hydroxyl groups are 0.1:1-100:1 (mole/mole) under solvent or solvent-free conditions at a temperature of 20-150 °C, preferably 50-100 °C. Ratio in the range, preferably in the range of 0.5:1-50:1 (mole/mole), preferably in the range 1:1-10:1 (mole/mole), preferably in the range 1:1-3 It can be reacted with aliphatic, alicyclic, aromatic or aromatic-aliphatic di-, tri- and poly-isocyanates in a ratio in the range of :1 (mole/mole). However, the ratio of (meth)acrylated polyol and di-, tri- and poly-isocyanate is not limited in the reaction. The organic solvent can be selected from DMF, DMSO, pyridine, hydrocarbon and cyclic hydrocarbon, alkyl ester, alcohol, ketone and mixtures thereof, but is not limited to the reaction. The organic solvent may preferably be used in a ratio of 1 to 3000%, preferably 50 to 1000%, relative to the (meth)acrylated polyol.

6. Use of urethane-based materials for different applications

Urethane-based materials functionalized with (meth)acrylates can be used for different applications, such as plastics, crosslinkers, resins, coatings, and (3D)-printing by photo-induced polymerization. They are polymerized with any initiator under solvent and solvent-free conditions by a photo-induced process at a temperature of 10-200°C, preferably 30-100°C. However, the ratio and form of initiator are not limited in polymerization. The organic solvent can be selected from DMF, DMSO, pyridine, hydrocarbon and cyclic hydrocarbon, alkyl ester, alcohol, ketone and mixtures thereof, but is not limited to the reaction. The organic solvent may preferably be used in a ratio of 1 to 3000%, preferably 50 to 1000%, relative to the (meth)acrylated polyol.

Meanwhile, the present invention is further described in more detail with reference to the following examples. However, these examples should not be construed as limiting the scope of the invention in any way.

Quantitative analysis of the reaction components of the examples was performed using gas chromatography (GC, Varian 430-GC, Varian, USA) equipped with a FactorFour capillary column, VF-1ms (Varian, 15M×0.25 mm) and a flame ionization detector. Did. The initial column oven temperature was increased from 50C to 250C at a rate of 20 C/min or 40C/min. Samples diluted to a final concentration of 0.1-2 mg/mL using acetonitrile were injected in a split injection mode of 10% at 275C. Substrate conversion and product ratio were calculated by comparing the peak area of the gas chromatogram.

The formation of linear carbonate groups from the cyclic carbonates of the examples was determined from samples collected from polymerized material by FT-IR analysis. Spectra of the samples were obtained in the region of 500-4000 cm ^-1 using Nicolet-iS5 (Thermo Scientific, USA). The air background spectrum was collected prior to sample analysis and subtracted from each sample spectrum.

Example 1. Preparation and separation of mono- and di-methacrylated trimethylolpropane

134 g (1 mole) of trimethylolpropane and 86 g (1 mole) of methacrylic acid are 4 g of p-toluenesulfonic acid, 1 g of p-methoxyphenol and 1 L of a water-immiscible solvent such as benzene, toluene and ethyl Acetate) into a 2L reaction vessel. The reaction was carried out with increasing temperature to 80°C for 15 hours. Once about 75% trimethylolpropane was consumed in the GC analysis (Figure 2(A)), the reaction was quenched and cooled to room temperature with the addition of 250 mL water. In this situation, an undesired by-product, tri-methacrylated trimethylolpropane, was formed only in trace amounts in the GC chromatogram.

Example 2. Separation of mono- and di-methacrylated trimethylolpropane

The solution obtained in Example 2 was extracted by a liquid-liquid extraction method in the first extraction, and was divided into a first aqueous phase and a first organic phase. After extracting the first aqueous phase, 250 mL water was added to the first organic phase and extracted in the same way. After performing a total of 10 extractions, all the first aqueous phases were pooled (FIG. 2(C)), and secondary extraction was performed with 300 mL organic solvent, dichloromethane. After a total of three extractions, the second organic phase was pooled (Fig. 2(E)), dried with 100 g of molecular sieve, and concentrated by simple evaporation. 124 g of mono-methacrylated trimethylolpropane (98% purity, FIG. 2(F)) was obtained from the second organic phase in the secondary extraction. The first organic phase resulting from the primary extraction (FIG. 2(B)) was dried with 50 g of molecular sieve, and 34 g of di-methacrylated trimethylolpropane (96% purity, FIG. 2(G)) Obtained by simple evaporation.

Example 3. Preparation and separation of mono- and di-methacrylated trimethylolpropane (2)

The same reaction as in Example 1 and the same separation as in Example 2 were performed except that the reaction was performed at 90°C for 3 hours. 84 g of mono-methacrylated trimethylolpropane (98% purity) was obtained from the second organic phase in the secondary extraction. 24 g of di-methacrylated trimethylolpropane (95% purity) was obtained from the first organic phase in the primary extraction.

Example 4. Preparation of methacrylated urethane

The 270 mg (1 mmole) di-methacrylated trimethylolpropane obtained in Example 1 was reacted with 87 mg (0.5 mmole) of toluene 2,4-diisocyanate in a 4 mL glass vial for 1 hour at 70 °C. . The reaction was monitored by FT-IR. 3(A) is an FT-IR spectra of di-methacrylated trimethylolpropane. Fig. 3B is the FT-IR spectra of toluene 2,4-diisocyanate. 3(C) is the FT-IR spectra of the reaction component and the diurethane product formed after 1 hour of reaction of di-methacrylated trimethylolpropane and toluene 2,4-diisocyanate at 80°C.

Example 5. Preparation of methacrylated polyurethane

The 202 mg (1 mmole) mono-methacrylated trimethylolpropane obtained in Example 1 was reacted with 174 mg (1 mmole) of toluene 2,4-diisocyanate in a 4 mL glass vial for 1 hour at 70°C. . The reaction was monitored by FT-IR. 4(A) is the FT-IR spectra of mono-methacrylated trimethylolpropane. Fig. 4B is the FT-IR spectra of toluene 2,4-diisocyanate. Figure 4 (C) is the FT-IR spectra of the polyurethane product formed after 1 hour of reaction of the reaction component and mono-methacrylated trimethylolpropane and toluene 2,4-diisocyanate at 80 °C.

Features, structures, effects, and the like described in the above-described embodiments are included in at least one embodiment of the present invention, and are not necessarily limited to only one embodiment. Furthermore, features, structures, effects, and the like exemplified in each embodiment may be combined or modified for other embodiments by a person having ordinary knowledge in the field to which the embodiments belong. Therefore, the contents related to such combinations and modifications should be interpreted as being included in the scope of the present invention.

In addition, although the embodiments have been mainly described above, these are merely examples and do not limit the present invention, and those skilled in the art to which the present invention pertains are exemplified above in a range that does not depart from the essential characteristics of the present embodiment. It will be appreciated that various modifications and applications are possible. For example, each component specifically shown in the embodiments can be implemented by modification. And differences related to these modifications and applications should be construed as being included in the scope of the invention defined in the appended claims.

Claims (3)

Reacting triol and (meth)acrylate;
Primary extraction by adding water to the partial (meth)acrylated polyol prepared from the reacting step;
In the first extraction step, the first organic phase and the first aqueous phase are separated, and obtaining a di-(meth)acrylated polyol from the first organic phase;
Second extraction by adding a solvent to the first aqueous phase;
In the second extraction step, the second organic phase and the second aqueous phase are separated,
Obtaining a mono-(meth)acrylated polyol from the second organic phase; And
A method of separating a partial (meth)acrylated polyol comprising the step of obtaining a residual polyol from the second aqueous phase.
According to claim 1,
The water separation method of the partial (meth) acrylated polyol, characterized in that contained in a ratio of 5 to 500% relative to the partial (meth) acrylated polyol.
According to claim 1,
The primary extraction step is a method of separating partial (meth) acrylated polyols, characterized in that repeated 1 to 15 times.

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