KR100924966B1 - Method for preparing an acetoacetate resin - Google Patents

Abstract

In the method for producing acetoacetate resin, 15 to 80% by weight of polyester polyol and 3 to 40% by weight of diisocyanate and 10 to 65% by weight of acetoacetate monomer containing acetoacetate group are mixed to form a mixture. The polyester polyol and diisocyanate are reacted in the mixture to form a urethane modified polyester polyol. Next, the urethane-modified polyester polyol and acetoacetate monomer are transesterified to obtain acetoacetate. Acetoacetate resin obtained by the above method is a compound which is excellent in room temperature and low temperature curability and environmentally friendly.

Description

Method for preparing acetoacetate resin {Method for preparing an acetoacetate resin}

The present invention relates to a method for producing acetoacetate resin. More specifically, the present invention relates to a method for producing acetoacetate resin that can be used for flooring, coating or adhesives.

Conventionally used two-component resin curing systems include epoxy-amine systems and urethane systems. Such urethane systems include isocyanate-polyols and isocyanate-amine systems.

The epoxy-amine system is not only excellent in compressive strength, tensile strength, impact resistance and adhesion, but also excellent in a variety of chemicals and solvents. Due to these properties, the epoxy-amine system is used not only for flooring but also for repairing, finishing, protective coating and decorative coating of metal, aluminum, galvanized, wood and concrete in marine, aircraft, construction, etc. have. However, it lacks mechanical properties such as toughness and flexibility, and lacks resistance to sunlight and weathering. In addition, environmental problems are caused by phenol-based raw materials and chlorine, bromine and bisphenol-A of epoxy resins, which are harmful to humans when designing a solventless system.

On the other hand, the urethane system may exhibit rubber-like properties in high hardness materials according to mechanical properties such as toughness, flexibility, chemical resistance, low temperature curing, corrosion resistance and adhesion, and has excellent chemical properties. Due to these characteristics, urethane systems have been applied in many fields, and in particular, various applications such as paint, foam, flooring, waterproofing and sealing materials. However, during curing, there is a problem in that carbon dioxide gas is generated by moisture in the atmosphere, and thus foaming phenomenon occurs in the coating film. In addition, the use of plasticizer dioctylphthalate, heavy metal lead containing catalyst, chlorine group containing 4.4'-methylene bis-orthochloroaniline (4.4'-METHYLENE BIS-ORTHO CHLORO ANILINE, MOCA), etc. It is occurring.

In order to solve the above problems, although the use of low-viscosity liquid epoxy in the epoxy system reduces the use of phenolic raw materials, the epoxy system contains chlorine because epichlorohydrin is used in the preparation of epoxy resins. It must be. Therefore, an environmental problem due to the chlorine occurs. In addition, the urethane system uses a variety of other plasticizers, including dioctyl adipate, but the plasticizers are very expensive. The catalyst may also use bismuth or zinc, not lead, but has a disadvantage in that the performance is not satisfactory and the cost is high. In addition, fatty acid-modified polyols and the like are used in place of the MOCA, but this is also expensive.

Therefore, there is a need for a resin curing system having a low cost and hardly causing environmental problems. In addition, new main resins included in the above resin curing systems are required.

An object of the present invention is to provide a method for producing an acetoacetate resin composition which is suitable for being used as a main resin of a solvent-free resin curing system, which is environmentally friendly and has a low viscosity.

Acetoacetate resin composition according to an embodiment of the present invention for achieving the above object, acetoacetate monomer containing 15 to 80% by weight of polyester polyol, 3 to 40% by weight of diisocyanate and acetoacetate group Mix the 10 to 65% by weight to prepare the mixture. The polyester polyol and diisocyanate are reacted in the mixture to form a urethane modified polyester polyol. Next, the urethane-modified polyester polyol and the acetoacetate monomer are transesterified to obtain an acetoacetate resin composition.

According to one embodiment of the present invention, the polyester polyol has a hydroxyl group equivalent weight of 30 to 2000.

According to one embodiment of the present invention, the diisocyanate has an isocyanate equivalent weight of 84 to 200.

According to one embodiment of the invention, the diisocyanate is hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicycloheximethane diisocyanate, tetramethylxyl Examples of the diisocyanate, xylene diisocyanate, toluene diisocyanate and the like can be given. These may be used alone or in combination.

According to one embodiment of the present invention, the acetoacetate monomer may be exemplified by ethyl acetoacetate, butyl acetoacetate, tertiary butyl acetoacetate, and the like. These may be used alone or in combination.

According to one embodiment of the present invention, the urethane-modified polyester polyol may be formed by reacting the polyester polyol and the diisocyanate in an equivalent ratio of 1: 0.1 to 0.8.

According to one embodiment of the invention, the reaction for forming the urethane-modified polyester polyol may be carried out at a temperature of 60 to 90 ℃.

According to one embodiment of the invention, the transesterification may be carried out at a temperature of 100 to 180 ℃.

According to one embodiment of the present invention, tertiary butyl alcohol produced by the transesterification can be removed.

The acetoacetate resin composition prepared by the method of the present invention described above is suitable for use as a main resin of a solvent-free resin curing system. In particular, when using the resin hardening system which uses the said acetoacetate resin composition as a main resin, it is excellent in normal temperature and low temperature hardenability. Moreover, since chlorine is not contained in the said main resin, since a chlorine compound is not detected in a coating film, it is very environmentally friendly.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

The acetoacetate resin composition of the present invention is prepared by reacting a polyester polyol with an isocyanate to synthesize a urethane-modified polyester polyol, and then transesterifying the acetoacetate monomer to the urethane-modified polyester polyol.

It is preferable that the said polyester polyol is 30-2000 hydroxyl equivalent. When using a trifunctional polyol as said polyester polyol, the viscosity of a completed resin composition will raise too much. Therefore, it is preferable to use a bifunctional polyol as said polyester polyol. However, in some cases, you may use the trifunctional polyol marketed by the said polyester polyol. The polyester polyol may be a polyol itself consisting of ethylene glycol, propylene glycol, butylene glycol, hexanediol, methyl propanediol, neopentyl glycol, methylpentanediol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, At least one selected from the group of polyols listed above and adipic acid, azelaic acid, fumaric acid, maleic hydride, phthalic hydride, isophthalic acid, terephthalic acid, trimeletic anhydride, cyclohexyl die At least one selected from the group of polyacids consisting of seeds may be used as obtained by dehydration condensation.

The said polyester polyol can also be used as a commercially available product. Examples of commercially available products include the K-Flex family of polyester polyols of King Industry of the United States and the family of polyester polyols of Desmophen of Bayer, Germany. More specifically, products such as K-Flex 171-90, 128, 148, 188 (trade name) of King Industries Co., Ltd., and Desmophen 1100, 1200, 1300, 1652 (trade name) of Bayer Corporation can be used.

When the content of the polyester polyol contained in the acetoacetate resin composition of the present invention is less than 15% by weight, the resin composition becomes excessively high in viscosity. On the other hand, when the content of the polyester polyol exceeds 80% by weight, the surface dryness is lowered. Therefore, the polyester polyol preferably has 15 to 80% by weight, more preferably about 40 to 80% by weight relative to the acetoacetate resin.

It is preferable that the isocyanate equivalent is 84-200, and, as for the said diisocyanate, it is more preferable that it is 84-125. Examples of the diisocyanate that can be used include hexamethylene diisocyanate, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicycloheximethane diisocyanate, tetramethylxylene diisocyanate, xyl Rendiisocyanate, isophorone diisocyanate, etc. are mentioned. These may be used alone or in combination. In view of economics, it is preferable to use inexpensive yellowing toluene diisocyanate among the diisocyanates.

When the content of the isocyanate contained in the acetoacetate resin composition of the present invention is less than 3% by weight, the toughness and elasticity of the coating film are lowered. On the other hand, when the content exceeds 40% by weight, the resin composition causes a problem of high viscosity. Therefore, the isocyanate preferably has 3 to 40% by weight based on the acetoacetate resin. More preferably, it has 5-30 weight% with respect to the acetoacetate resin.

The acetoacetate monomer has a molecular weight of 130 to 158. Examples of the acetoacetate monomers include ethyl acetoacetate, butyl acetoacetate, tertiary butyl acetoacetate, and the like. These may be used alone or in combination. Among the acetate monomers listed above, it is preferable to use tert-butyl acetoacetate which causes the smoothest transesterification reaction.

When the content of the acetoacetate monomer contained in the acetoacetate resin composition is less than 10% by weight, the reactivity of the cured product is lowered. On the other hand, when the content exceeds 65% by weight, the degree of curing of the coating film is reduced. Therefore, the acetoacetate monomer preferably has 10 to 65% by weight based on the acetoacetate resin composition. More preferably, it has 15 to 40 weight%.

The polyester polyols, isocyanates and acetoacetate monomers are mixed in the respective weight percents as described. Next, the mixture is urethane reacted with the polyester polyol and the isocyanate at a temperature of 60 to 90 ° C. to form a urethane-modified polyester solution. The urethane-modified polyester polyol is formed by reacting the polyester polyol and the diisocyanate in an equivalent ratio of 1: 0.1 to 0.8.

Thereafter, the urethane-modified polyester solution and the acetoacetate monomer are transesterified at a temperature of 100 to 180 ° C. to obtain acetoacetate resin. The exchange reaction may be carried out while varying the temperature within the temperature range of 100 to 180 ° C. Specifically, the exchange reaction may be carried out while gradually increasing the temperature. Tertiary butyl alcohol is produced through the transesterification reaction, and acetoacetate resin is prepared by removing the tertiary butyl alcohol.

The acetoacetate resin produced by the same method as described above has an equivalent weight of 140 to 2000 mgKOH / g number average molecular weight of 280 to 6000. In addition, the acetoacetate resin produced by the above method is suitable for use as the main resin of a solvent-free resin curing system.

In addition, the acetoacetate resin may be cured at room temperature and low temperature by mixing a curing agent comprising an acrylate composition and a strong base catalyst. Therefore, the acetoacetate resin can be used for applications such as flooring, coating or adhesive.

Hereinafter, the present invention will be described in more detail through preferred embodiments of the present invention, but the present invention is not limited thereto.

Acetoacetate Resin Manufacture

Example 1

Into a flask equipped with a thermometer, a condenser, a water separator, and a stirrer, an initial additive of K-Flex 171-90 (trade name of King Industries, Inc.) 3000g, toluene diisocyanate 174g, tertiary butyl acetoacetate was added in order It heated up to 80 degreeC. Thereafter, the urethane reaction was performed for 2 hours while the temperature was elevated. Next, the transesterification reaction was carried out by raising the temperature to 110 ° C. and then slowly raising the temperature to 160 ° C. over 3 hours. The tertiary butyl alcohol from the water separator was continuously recovered during the temperature increase. After the temperature was raised to 160 ° C., the recovery of tertiary butyl alcohol was confirmed to terminate the reaction when 90% of the theoretical amount was exceeded to obtain an acetoacetate resin. The acetoacetate resin obtained in this way had an acetoacetate equivalent of 878 mgKOH / g, a Gardner viscosity (25 ° C) of Z7 +, and a number average molecular weight of 3500.

Example 2

Into the flask equipped with a thermometer, a condenser, a water separator, and a stirrer, 186 g of ethylene glycol having a hydroxy group equivalent of 31 mgKOH / g, 174 g of toluene diisocyanate, and 632 g of tertiary butyl acetoacetate were added in this order, and the temperature was raised to about 80 ° C. . Thereafter, the urethane reaction was performed for 2 hours while the temperature was elevated. Next, the transesterification reaction was carried out by raising the temperature to 110 ° C. and then slowly raising the temperature to 160 ° C. over 3 hours. The tertiary butyl alcohol from the water separator was continuously recovered during the temperature increase. After the temperature was raised to 160 ° C., the recovery of tertiary butyl alcohol was confirmed to terminate the reaction when 90% of the theoretical amount was exceeded to obtain an acetoacetate resin. The acetoacetate resin obtained in this way had an acetoacetate equivalent of 174 mgKOH / g, a Gardner viscosity (25 ° C.) of Y +, and a number average molecular weight of 700.

Example 3

Into a flask equipped with a thermometer, a condenser, a water separator, and a stirrer, K-Klex 1440g having a hydroxyl equivalent of 240mgKOH / g, 174g of toluene diisocyanate, and 632g of tertiary butyl acetoacetate were added to the flask, and then heated up to about 80 ° C. It was. Thereafter, the urethane reaction was performed for 2 hours while the temperature was elevated. Next, the transesterification reaction was carried out by raising the temperature to 110 ° C. and then slowly raising the temperature to 160 ° C. over 3 hours. The tertiary butyl alcohol from the water separator was continuously recovered during the temperature increase. After the temperature was raised to 160 ° C., the recovery of tertiary butyl alcohol was confirmed to terminate the reaction when 90% of the theoretical amount was exceeded to obtain an acetoacetate resin. The acetoacetate resin obtained in this manner had acetoacetate equivalent weight of 488 mgKOH / g, a Gardner viscosity (25 ° C) of Z4, and a number average molecular weight of 2000.

The hardened | cured material was produced by mixing a hardening | curing agent with the acetoacetate resin obtained by the manufacturing method of the said Examples 1-3. Specifically, the mixture was mixed with HDDA (hexanediol diacrylate), TMPTA (trimethanol propane triacrylate), and the like, and cured with an organic strong base, TMG (Tetra methyl guanidine) catalyst. The compounding table which mixed the hardening | curing agent with the acetoacetate resin of the said Examples 1-3 is shown in Table 1 below.

[Table 1] (Unit: parts by weight)

Cured product 1 Cured product 2 Cured product 3 Example 1 878 Example 2 174 Example 3 488 HDDA 49 49 49 TMPTA 56.5 56.5 56.5 TMG 3 3 3

When the curing agent was mixed as described above, the resins of Examples 1 to 3 were found to have good room temperature and 5 ° C. curing properties. As such, the resins of Examples 1 to 3 may be used as an adhesive, a coating material, a waterproofing material, and a flooring material because they may be cured using the acrylate composition and the strong base catalyst as a curing agent.

The acetoacetate resin prepared by the method of the present invention and a cured product including the same are environmentally friendly resin compounds having excellent room temperature and low temperature curability, solvent-free, and no chlorine compounds detected. In addition, the acetoacetate resin produced by the method of the present invention can be used as an adhesive, a flooring material and a waterproofing material by curing with a curing agent.

Claims (9)

The urethane-modified polyester is reacted by reacting the polyester polyol and the diisocyanate in a mixture comprising 15 to 80 wt% of polyester polyol, and 10 to 65 wt% of acetoacetate monomer containing 3 to 40 wt% of diisocyanate and acetoacetate group. Forming a polyol; And  A method for producing acetoacetate resin, characterized in that the step of transesterifying the urethane-modified polyester polyol and acetoacetate monomer to obtain acetoacetate. The method for producing acetoacetate resin according to claim 1, wherein the polyester polyol has a hydroxyl group equivalent of 30 to 2000. The method for preparing acetoacetate resin according to claim 1, wherein the diisocyanate has an isocyanate equivalent weight of 84 to 200. The diisocyanate of claim 1, wherein the diisocyanate is hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicycloheximethane diisocyanate, tetramethylxylene diisocyanate, Acetoacetate resin production process comprising at least one selected from the group consisting of xylene diisocyanate and toluene diisocyanate. The method of claim 1, wherein the acetoacetate monomer comprises at least one selected from the group consisting of ethyl acetoacetate, butyl acetoacetate and tertiary butyl acetoacetate. The method for producing acetoacetate resin according to claim 1, wherein the urethane-modified polyester polyol is formed by reacting the polyester polyol and the diisocyanate in an equivalent ratio of 1: 0.1 to 0.8. The method for producing acetoacetate resin according to claim 1, wherein the reaction for forming the urethane-modified polyester polyol is performed at a temperature of 60 to 90 ° C. The method of claim 1, wherein the transesterification is carried out at a temperature of 100 to 180 ℃ acetoacetate resin production method. The method for preparing acetoacetate resin according to claim 1, further comprising removing tertiary butyl alcohol produced by the transesterification reaction.