KR20050075186A - Monomers and polymers containing rosin, and method for preparing thereof - Google Patents

Abstract

The present invention relates to rosin monomers, rosin homopolymers, rosin copolymers and methods for their preparation. More specifically, the present invention relates to a rosin-based monomer having a hydroxyl group in a molecule thereof by reacting a rosin with an acrylic monomer having an epoxy group in the presence of a catalyst and a method for producing the same. The present invention also relates to a homopolymer and a copolymer prepared by using a rosin-based monomer, and has a feature of preparing a rosin-based polymer having a high molecular weight and a high yield. In addition, since the rosin-based monomer and polymer of the present invention have a hydroxyl group (-OH group) in the molecule, the hydroxyl group present on the surface of the inorganic oxide when applied to the paint industry or the composite material industry and the hydroxyl period present in the rosin-based monomer of the present invention. The strong interaction of (hydrogen bond, miscibility) has the effect of excellent dispersibility, storage stability and mechanical properties.

Description

Rosin-based monomers, rosin-based resins and a method for producing the same {Monomers and polymers containing rosin, and method for preparing Technical}

The present invention relates to novel rosin-based monomers used in the production of adhesives, photosensitizers and the like and methods for their preparation. The present invention also relates to homopolymers and copolymers of the rosin-based monomers.

Rosin is a natural product composed of various isomers and analogues having one carboxyl group and two carbon-carbon double bonds. Rosin and its analogues have excellent adhesion, water resistance, wear resistance, and excellent gloss. Therefore, they are widely used to supplement the physical properties by adding to the polymer material. Conventionally, rosin of natural materials has been used as additives such as adhesion promoters, paints, synthetic rubber emulsifiers, paints and paper sizing agents, but rosin, which is a natural substance, has a problem in that its use is limited.

Recently, in order to solve the problem that the use of natural rosin is limited due to its low molecular weight, it is possible to introduce a polymerizable functional group into rosin, a natural substance, and then copolymerize the rosin compound in which the functional group is introduced with a homopolymer or other comonomer. The method of using water is used. For example, in US Pat. No. 3,206,440, a rosin derivative obtained by Diels-Alder reaction of maleic anhydride and rosin in order to take advantage of the reactivity of an anhydride portion is prepared. The method to use for such use is shown.

However, the above method has a problem that the theoretical reaction yield of maleic anhydride and rosin is 54%, and the process is complicated. The low yield is due to the composition of isomers that can react with maleic anhydride among the various isomers of rosin.

In addition, some studies on the synthesis of rosin polymers have been reported. For example, polyamideimide and polyester containing rosin moiety were prepared from rosin-maleic acid adducts and from rosin moiety-containing nonconjugated vinyl monomers. However, the molecular weight of these polymers was very low due to the bulky rosin moiety. Therefore, there is a demand for the development of a method for producing a new rosin derivative having a higher molecular weight than rosin, which is a natural material and copolymerizable with various comonomers as well as homopolymerization.

In addition, the paint industry, which is one of the fields of using rosin, is mostly composed of a mixture system of a polymer component and an inorganic oxide, and the inorganic oxide must be uniformly dispersed in the polymer component. The existing rosin derivatives have a problem in that precipitation of inorganic oxides occurs due to low miscibility with inorganic oxides, difficulty in uniform dispersion, and low long-term stability. Therefore, it is required to improve the dispersibility and long-term storage stability by improving the wettability of the inorganic oxide.

The present invention has been designed to solve the above problems, and has the characteristics of producing a high molecular weight and high yield rosin derivatives, unlike the prior art, homopolymerization as well as copolymerization with various comonomers It is to provide a rosin-based monomer and a method for producing the same. It is also an object of the present invention to provide such rosin-based homopolymers and copolymers. In particular, in order to improve the miscibility (wetting) of inorganic oxides required for the paint industry, a rosin-based monomer having a hydroxyl group was devised. In the present invention, when reacted with an acrylic monomer having a rosin and an epoxy group, a hydroxyl group (-OH group) The discovery of a new fact that rosin derivatives with The rosin homopolymer or copolymer of the present invention having such a hydroxyl group has a simple interaction between the hydroxyl group present on the surface of the inorganic oxide and the hydroxyl period present on the rosin monomer of the present invention when applied to the paint industry or the composite material industry (hydrogen bond). The present invention was completed by focusing on excellent dispersibility, storage stability, and mechanical properties.

The present invention can be copolymerized with monomers of acrylic monomers, thermosetting and photocurable materials as well as homopolymerization, rosin-based monomers having a hydroxyl group in the molecule, rosin-based resins (rosin-based homopolymers and rosin-based copolymers) and their preparation A method for solving the above technical problem is provided.

According to an aspect of the present invention there is provided a formula (3) prepared by reacting a rosin of the formula (1) with an acrylic monomer having an epoxy group, such as formula (2) and a method for producing the same.

<Formula 1>

<Formula 2>

(In Formula 2, R is selected from hydrogen (H) or methyl group (-CH ₃ ).)

<Formula 3>

 (In Formula 3, R is the same as defined in Formula 2.)

In addition, according to an aspect of the present invention provides a copolymer obtained by copolymerizing the above-mentioned formula (3) homopolymerized with the above-described formula (3) and a comonomer.

The method for preparing Formula 3, which is a rosin derivative of the present invention, will be described in more detail with reference to FIG. 1. First, the synthesis of rosin monomers may be achieved by dissolving the rosin of Formula 1 and the compound of Formula 2 in a solvent, followed by heating and stirring by adding a catalyst and a polymerization inhibitor.

The rosin that can be used to prepare the rosin-based monomer of the present invention may be any of gum rosin, wood rosin and tall oil rosin, and is not related to the content of isomers. Compounds of formula (2) usable for the preparation of rosin monomers include glycidyl methacrylate and glycidylacrylate having an epoxy group. In addition, the catalyst usable in the preparation of the rosin-based monomer of the present invention may be an alkaline substance such as tetraalkylammonium halide, tetra methylammonium hydroxide, benzyltrimethyl ammonium hydroxide, and it is suitable to use 10 to 200 mol% of the reactants. Generally the polymerization inhibitor which can be used for manufacture of the rosin-based monomer of the present invention is preferably parabenzo quinone or hydroquinone, but the polymerization inhibitor is not particularly limited. The reaction solvent is preferably methyl ethyl ketone, benzene, benzene chloride or the like, but it is not necessary to define it as one solvent.

A method of preparing a rosin homopolymer by homopolymerizing the rosin derivative prepared by the above method will be described. First, the rosin-based monomer of Formula 3 may be dissolved in a solvent such as benzene or dimethylformamide, and a radical polymerization may be performed by adding a polymerization initiator to prepare a rosin-based homopolymer. Specifically, rosin monomers produced after radical polymerization at a temperature of 10 to 80 ° C. for 24 hours using 0.05 to 3% by weight of a radical initiator such as N, N'-azobisisobutylonitrile (hereinafter referred to as AIBN) as a polymerization initiator. The polymer is precipitated in nonsolvent, filtered and dried. In addition, the rosin derivative of Formula 3 may be anion polymerized in the presence of an anion initiator to prepare a rosin homopolymer.

The polymerization vessel used for the production of the rosin homopolymer should be a container that can block external oxygen, but if not blocked, the polymerization should be continued while injecting nitrogen. It is preferable to use benzene as the polymerization solvent to be used, but any solvent capable of dissolving the monomer may be used, and bulk polymerization without solvent may be possible.

Meanwhile, a method of preparing a rosin-based copolymer using the rosin derivative and the comonomer of Formula 3 will be described. The method of preparing the rosin-based copolymer is the same as the method of preparing the rosin-based homopolymer described above, except that radical polymerization of the rosin-based monomer of Formula 3 and a plurality of vinyl monomers, such as second and third, as a comonomer at the same time is different. . When used for the use of adhesives and compatibilizers, it is preferable to react with the rosin derivative of the formula (3) and styrene, hexyl acrylate, glycidyl methacrylate, methyl methacrylate, acrylic acid or methyl methacrylate.

When used for applications such as ultraviolet curing adhesives, thermosetting adhesives and photoresist (co), it is preferable to copolymerize the rosin monomer of the formula (3) with a thermosetting or photocurable monomer. As the photocurable material, a monomer having cinnamoyloxymaleimide or cinnamoyl group or styrylpyridyl group may be used. In addition, a vinyl monomer having an epoxy group may be used as the thermosetting material.

Formula (3) of the present invention and the rosin-based homopolymer and the rosin-based copolymer prepared therefrom exhibited excellent mechanical and physical properties because not only the adhesion by the rosin group but also the hydroxyl group (-OH) in the molecule. It was confirmed that the rosin-based monomer having a new structure and the polymer thereof according to the present invention have a hydroxyl group, and thus have excellent mechanical and physical properties by hydrogen bonding between the hydroxyl groups.

In general, paints, composite materials and the like are largely composed of a polymer component and an inorganic additive (mainly an inorganic oxide). These inorganic additives must be evenly dispersed throughout the polymer component to exhibit the desired physical properties. In the industrial field, various dispersants and additives are used to uniformly disperse the inorganic additive in the polymer component, but there are limitations in uniformly dispersing the inorganic additive. In addition, if long-term storage is required, such as paint, there should be no precipitation of inorganic additives. Such dispersibility and sedimentation stability may be influenced by the wettability of the surface of the polymer component and the inorganic additives, and the dispersibility of the inorganic additives may be excellent and the sedimentation stability may be secured only when the wettability is excellent.

The rosin homopolymer and the rosin copolymer prepared from Chemical Formula 3 of the present invention have a hydroxyl group in the molecule. In addition, the surface of the inorganic additive used in the paint industry or the composite material field described above has most of hydroxyl groups. Therefore, the rosin homopolymer and the rosin copolymer of the present invention, when mixed with the inorganic additive, dispersibility by the interaction (hydrogen bond, compatibility) of the hydroxyl group included in the polymer of the present invention and the hydroxyl group included in the inorganic additive It was excellent and sedimentation stability was also excellent.

The rosin-based monomers and polymers (or copolymers) according to the present invention have another feature that they themselves exhibit photosensitivity. In other words, it has the possibility of application as a photoresist. 2 is a result of irradiating the absorbance change with Shimadzu UV-2100 spectrophotometer after dissolving the polymer in a solvent such as benzene (or coating on a quartz plate and drying to form a thin film) and then irradiating with a high pressure mercury lamp. This is showing up.

 As described above, the rosin-based monomer and the polymer (or copolymer) prepared therefrom are not only new structures of which the structure is known, but also have hydroxyl groups in the molecule. When applied to the industrial field used mixed with the oxide there was an advantage to obtain excellent dispersibility and sedimentation stability. In addition, since the polymer itself has photosensitivity, it is also possible to apply to the electronics industry.

EXAMPLES The present invention will be described below in detail with reference to Examples of the present invention, but the present invention is not limited to the following Examples.

Example 1: Preparation of Rosin Monomer

15 g (5.0 × 10 ^-2 mol) of purified abietic acid, 8.3 ml (6.6 × 10 ^-2 mole) of glycidylmethacrylate (GMA), 0.38 g of catalyst tetramethylammonium bromide, 130 ml of solvent methyl ethyl ketone (MEK) and polymerization inhibitor 0.07 g of hydroquinone was added to a three-necked flask and reacted at 70 ° C. for 3 hours with stirring in a nitrogen stream. The reaction product was decompressed at 40 ° C. to remove MEK, the reaction solvent. The reaction product was heated to 50 ° C. to remove unreacted GMA, and the product was washed twice with water to remove unremoved GMA and reaction solvent. Subsequently, two washings were performed with an aqueous solution of caustic soda at pH 9 to remove unreacted abietic acid, thereby preparing a rosin-based monomer (hereinafter referred to as AMA).

Example 2: Preparation of rosin homopolymer

1 g (2.3 × 10 ^-3 mol) of rosin-based monomer AMA synthesized in Example 1 in a 30 ml ampoule, 0.003 g of AIBN corresponding to 1 mol% based on the number of monomer moles were 2.3 ml of dimethylformamide (DMF), benzene, and tetrahydrofurane (THF). It was dissolved in each and degassed by thraw-freeze method, and then melted and put in a polymerization tank at 65 ° C for polymerization for 24 hours. After polymerization, the mixture was precipitated in 200 ml of a mixed solvent of methanol / acetone (v / v = 9), filtered, and dried to prepare a rosin homopolymer.

Example 3 and 4: Preparation of rosin copolymer

Copolymers of rosin derivatives were synthesized as shown in the schematic shown in FIG. 3. First, 1.1 g (8.9 × 10 ⁻³ mol) of AMA, which is one of the rosin-based monomers of the present invention, and methacrylate (MA), a comonomer, were dissolved in 4.5 ml of DMF. At this time, the feed ratio of AMA and MA was adjusted to 100: 10. In addition, 0.0015 g of AIBN corresponding to 0.1 mol% of the total number of moles of the two monomers were put in a polymerization tube, degassed by thraw-freeze method, and then sealed, and put in a polymerization tank at 65 ° C. for polymerization for 24 hours. After polymerization, precipitated in 300 ml of methanol, filtered and dried to prepare poly (AMA-co-MA). Synthesis was confirmed by NMR analysis, the results are shown in Figure 4a.

The preparation of poly (AMA-co-MMA) using methylmethacrylate (MMA) as comonomer was similar to that of poly (AMA-co-MA). 1.2 g (8.9 × 10 ^-3 mol) of the two monomers AMA and MMA, 4.5 ml of DMF as a solvent, and 0.0015 g of AIBN corresponding to 0.1 mol% of the number of moles of the two monomers together were placed in a polymerization tube, and thraw-freeze method. After degassing, it was melted, put in the polymerization tank at 65 degreeC, and it superposed | polymerized for 24 hours. At this time, the feed ratio of AMA and MMA was adjusted to 100: 10. After polymerization, poly (AMA-co-MMA) was prepared by precipitation in 300 ml of methanol, followed by filtration and drying. Synthesis was confirmed by NMR analysis, the results are shown in Figure 4b.

<Example 5: Analysis of physical properties of rosin copolymer>

The molecular weight of the copolymer of the rosin derivative synthesized in Examples 3 and 4 was measured by Waters GPC alliance 2100 gel-permeation chromatography by dissolving 0.02 g of a sample in 10 ml of THF. As a result, the molecular weight appeared in the range of 50,000 to 100,000, a high molecular weight rosin copolymer was obtained. In addition, the pyrolysis temperature was measured by Dupont 2100 thermogravimetric analyzer (TGA) at a rate of 30 ℃ / min under a nitrogen stream, it was completely decomposed at 400-470 ℃ excellent thermal stability.

As described above, the present invention relates to a rosin-based monomer, a rosin-based homopolymer, a rosin-based copolymer, and a method for preparing the same. Unlike the related art, a rosin derivative having a high molecular weight and a high yield can be prepared by the present invention. It has a characteristic. In addition, since the rosin-based monomers and polymers of the present invention have a hydroxyl group (-OH group) in the molecule, the hydroxyl period present in the surface of the inorganic oxide and the rosin-based monomer of the present invention when applied to the paint industry or the composite material industry The strong interaction of (hydrogen bond, miscibility) has the effect of excellent dispersibility, storage stability and mechanical properties.

Although the present invention has been described in detail only with respect to specific examples, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.

1 is a schematic view showing the preparation of the rosin monomer of the present invention.

Figure 2 is a graph showing the change in absorbance of the rosin-based polymer (resin) according to the ultraviolet irradiation time according to the present invention.

3 is a schematic view showing the preparation of the rosin-based copolymer according to the present invention.

Figure 4a is a graph showing the NMR analysis of the poly (AMA-co-MA) prepared by the method of Example 3 of the present invention.

Figure 4 b is a graph showing the results of NMR analysis of poly (AMA-co-MMA) prepared by the method of Example 4 of the present invention.

Claims (4)

Rosin-based monomer represented by the formula (3) and characterized in that the raw material of the rosin-based homopolymer and rosin-based copolymer <Formula 3> (In Formula 3, R is selected from hydrogen (H) or methyl group (-CH ₃ ).) In preparing a rosin-based monomer, a rosin of Formula 1 is prepared by reacting an acrylic monomer having an epoxy group with an alkali catalyst in the presence of an alkali catalyst, as shown in Formula 2 below. <Formula 1> <Formula 2> (In Formula 3, R is selected from hydrogen (H) or methyl group (-CH ₃ ).) <Formula 3> (In Formula 3, R is selected from hydrogen (H) or methyl group (-CH ₃ ).) Rosin-based homopolymers produced by polymerizing a rosin-based monomer of the following structural formula 3 alone in a rosin-based polymer <Formula 3> (In Formula 3, R is selected from hydrogen (H) or methyl group (-CH ₃ ).) In the copolymer obtained by copolymerizing the rosin-based monomer of the structural formula 3 and the second monomer, at least one selected from a monomer having a carbon-carbon double bond, a thermosetting material or a photocurable material is prepared. Characterized rosin copolymer <Formula 3> (In Formula 3, R is selected from hydrogen (H) or methyl group (-CH ₃ ).)