Lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product and its manufacturing method

Abstract

To provide a method for producing a lactone-modified hydroxyalkyl (meth)acrylate compound product with a low content of a di(meth)acrylate compound.SOLUTION: A method for producing a lactone-modified hydroxyalkyl (meth)acrylate compound includes reacting a hydroxyalkyl (meth)acrylate compound with a caprolactone compound in the presence of a dyiaryl phosphate represented by a formula (1). [Ar1, Ar2 each denote a substituted / unsubstituted aryl group; Ar1, Ar2 may bind to each other to form a ring with a (-O-P-O-) group].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to lactone-modified hydroxyalkyl (meth)acrylic acid ester compound products and methods for making same. [Background technology]

[0002] Acrylic paints, which are excellent in weather resistance, chemical resistance, and stain resistance and are suitable for coating, have been widely used in the fields of automobiles, home appliances, construction, etc. Among them, lactone-modified hydroxyalkyl (meth)acrylic esters having oxyalkylene repeating units, which are reaction products of hydroxyalkyl (meth)acrylic esters and lactones, have attracted attention as monomers capable of forming highly flexible coating films. However, the reaction between hydroxyalkyl (meth)acrylic esters and lactones is difficult to control, and there are problems such as side reactions that cause coloring and gelation.

[0003] In order to solve the above-mentioned problems in reaction control, metal catalysts and the like are used. For example, Patent Document 1 discloses a method for producing a reactive polymer using a reaction product of ε-caprolactone and a hydroxyalkyl (meth)acrylate as raw materials and other vinyl monomers, using stannous halide as a catalyst. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 1-25322 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when stannous halide is used as a catalyst, ester exchange between hydroxyalkyl (meth)acrylates tends to occur, resulting in the by-product of di(meth)acrylates that have high boiling points and are difficult to purify and separate. In curable resin compositions using lactone-modified hydroxyalkyl (meth)acrylic acid ester compound products containing such di(meth)acrylates as raw materials, there is a problem that three-dimensional crosslinking occurs during radical polymerization, resulting in a significant increase in viscosity or gelation.

[0006] Therefore, an object of the present disclosure is to provide a method for producing a lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product having a low content of di(meth)acrylate compounds. Another object of the present disclosure is to provide a lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product having a low content of di(meth)acrylate compounds. [Means for solving the problem]

[0007] As a result of intensive research to achieve the above-mentioned object, the inventors of the present disclosure have found that when a hydroxyalkyl (meth)acrylate compound is reacted with a cyclic ester compound in the presence of a specific amount of a diaryl phosphate, a lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product having a low content of di(meth)acrylate compound can be obtained.

[0008] That is, the present disclosure relates to a method for producing a hydroxyalkyl (meth)acrylate compound and a cyclic ester compound represented by the following formula (1): [ka] [In formula (1), Ar 1 , Ar 2 are the same or different and each represents an aryl group which may have a substituent. Ar 1 , Ar 2 may be bonded to each other to form a ring together with the (-OPO-) group. The present invention provides a method for producing a lactone-modified hydroxyalkyl (meth)acrylic ester compound product, comprising reacting a lactone-modified hydroxyalkyl (meth)acrylic ester compound in the presence of a diaryl phosphate represented by the following formula:

[0009] The present disclosure also relates to a compound represented by the following formula (4): [ka] [In formula (4), R 1 is hydrogen or a methyl group, R 2 It represents an alkylene group having 1 to 6 carbon atoms which may have a substituent.] The present invention provides a lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product having a content of a di(meth)acrylate compound represented by the following formula:

[0010] The present disclosure also provides a reactive oligomer comprising the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound in the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product as a monomer component.

[0011] The present disclosure also provides a curable resin composition comprising the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound in the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product and / or the reactive oligomer as a monomer component.

[0012] The present disclosure also provides a cured product of the curable resin composition. Effect of the Invention

[0013] According to the present disclosure, it is possible to produce lactone-modified hydroxyalkyl (meth)acrylic acid ester compound products having a low content of di(meth)acrylate compounds. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The manufacturing method of the present disclosure is a method for manufacturing a lactone-modified hydroxyalkyl (meth)acrylate compound product having a low content of di(meth)acrylate compound, which comprises subjecting a hydroxyalkyl (meth)acrylate compound and a cyclic ester compound to a ring-opening addition reaction in the presence of a diaryl phosphate represented by the following formula (1): The amount of the diaryl phosphate added is 10 to 300 ppm by weight based on the total amount of the hydroxyalkyl (meth)acrylate compound and the cyclic ester compound.

[0015] The term "(meth)acrylate" means "acrylate or methacrylate." The term "lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product" refers to a mixture containing a lactone-modified hydroxyalkyl (meth)acrylic acid ester compound, and is synonymous with the term "lactone-modified hydroxyalkyl (meth)acrylic acid ester composition." [ka]

[0016] In formula (1), Ar 1 , Ar 2 are the same or different and each represents an aryl group which may have a substituent. Ar 1 , Ar 2 may be bonded to each other to form a ring together with the (-OPO-) group.

[0017] The above Ar 1 and Ar 2 The aryl group is preferably an aryl group having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms. Specific examples include a phenyl group, a biphenylyl group, a naphthyl group, a phenanthrenyl group, and an anthracenyl group.

[0018] The above Ar 1 and Ar 2Examples of the substituent that may be possessed by the include halogen atoms (chlorine, bromine, iodine, etc.), alkyl groups having 1 to 4 carbon atoms (methyl group, ethyl group, etc.), halogenated alkyl groups having 1 to 4 carbon atoms (trifluoromethyl group, etc.), aryl groups having 6 to 14 carbon atoms (phenyl group, biphenylyl group, etc.), silyl groups substituted with alkyl groups having 1 to 4 carbon atoms and / or aryl groups having 6 to 14 carbon atoms (triphenylsilyl group, t-butyl-diphenylsilyl group, etc.), nitro group, and alkoxy groups having 1 to 4 carbon atoms (ethoxy group, methoxy group, etc.).

[0019] The above Ar 1 and Ar 2 Examples of the ring which may be formed by bonding to each other together with the (-OPO-) group include 5- to 7-membered rings.

[0020] Specific examples of the diaryl phosphate include diphenyl phosphate, dinaphthyl phosphate, dicresyl phosphate, di(4-nonylphenyl) phosphate, dibiphenyl phosphate, dichlorophenyl phosphate, etc. Among these, diphenyl phosphate is preferred.

[0021] The hydroxyalkyl (meth)acrylate compound is represented by the following formula (2). [ka]

[0022] In formula (2), R 1 is hydrogen or a methyl group, R 2 represents a linear alkylene group having 2 to 6 carbon atoms which may have a substituent. 2 The substituent which may be present is preferably a methyl group.

[0023] Above R 2 Specific examples include an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a pentylene group, and a hexylene group.

[0024] Specific examples of the hydroxyalkyl(meth)acrylate compound represented by the above formula (2) include 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxyhexyl(meth)acrylate, etc. Among them, 2-hydroxyethyl(meth)acrylate is preferred.

[0025] The cyclic ester compound is preferably a cyclic ester compound having 4 to 10 carbon atoms, and examples thereof include γ-butyrolactone, δ-valerolactone, ε-caprolactone, oxocane-2-one, η-caprylolactone, oxecan-2-one, and oxacycloundecane-2-one.

[0026] The content of the lactone-modified hydroxyalkyl (meth)acrylic ester compound represented by the following formula (3) in the above lactone-modified hydroxyalkyl (meth)acrylic ester compound product is preferably 99.0% by weight or more, more preferably 99.6% by weight or more, and even more preferably 99.8% by weight or more. Here, the lactone-modified hydroxyalkyl (meth)acrylic ester compound also includes the above hydroxy(meth)acrylic ester compound that is a raw material. [ka]

[0027] R in Equation (3) 1 and R 2 is R in the above formula (2). 1 and R 2 is the same as R 3 represents a linear alkylene group having 3 to 9 carbon atoms which may have a substituent, and n represents a value of 0.2 to 20.

[0028] Above R 3Examples of the substituent that may be possessed by the alkyl group include linear or branched alkyl groups having 1 to 12 carbon atoms (e.g., methyl, ethyl, isopropyl, etc.), alkoxy groups having 1 to 12 carbon atoms (e.g., methoxy, ethoxy, etc.), and halogen atoms (e.g., chlorine, bromine, iodine, etc.).

[0029] Above R 3 Specific examples of the alkyl group include a trimethylene group, a tetramethylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and a nonylene group, and among these, a pentylene group is preferable.

[0030] The above n is preferably a value of 0.2 to 20, more preferably a value of 0.4 to 15.0, and even more preferably a value of 0.7 to 12.0. When the above n is within the above range, the viscosity is not too high and is easy to handle, and flexibility tends to be easily obtained in the cured product made from the above lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product as a raw material. The above lactone-modified hydroxyalkyl (meth)acrylic acid ester compound has a molecular weight distribution because it is synthesized by utilizing ring-opening addition polymerization of a lactone compound. Therefore, the above value of n is an average value.

[0031] Examples of the components contained in the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product other than the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound include the following di(meth)acrylate compounds and the raw material hydroxyalkyl (meth)acrylic acid ester compounds.

[0032] In the above production method, the amount of the diaryl phosphate added is, for example, 10 to 300 ppm by weight, preferably 50 to 250 ppm by weight, and more preferably 100 to 200 ppm by weight, based on the total amount of the hydroxyalkyl (meth)acrylate compound and the cyclic ester compound. When the amount added is within the above range, a sufficient catalytic effect can be obtained, and side reactions can be easily suppressed.

[0033] In the above production method, the molar ratio of the hydroxyalkyl (meth)acrylate compound to the cyclic ester compound (cyclic ester compound / hydroxyalkyl (meth)acrylate compound) can be changed depending on the desired degree of ring-opening addition number for the cyclic ester compound, and is, for example, preferably 1.0 to 20.0, more preferably 1.0 to 15.0, and even more preferably 1.0 to 12.0.

[0034] In the above-mentioned production method, a free radical inhibitor may be used in combination to suppress the radical polymerization of the hydroxyalkyl (meth)acrylate compound, which is a raw material. Examples of the free radical inhibitor include substituted phenols (4-methoxyphenol, etc.), quinones (hydroquinone, benzoquinone, monomethylhydroquinone, etc.). The amount of the inhibitor added is preferably 0.01 to 0.20 parts by weight, more preferably 0.03 to 0.15 parts by weight, based on 100 parts by weight of the total amount of the hydroxyalkyl (meth)acrylate compound and the cyclic ester compound.

[0035] The above production method may be carried out in an oxygen atmosphere in order to suppress polymerization of the acrylic double bond of the hydroxyalkyl (meth)acrylate compound.

[0036] In the above-mentioned production method, in order to adjust the viscosity of the reaction solution, a solvent inactive to the cyclic ester compound and the hydroxyalkyl (meth)acrylate compound may be added. Examples of the solvent include aromatic hydrocarbons (toluene, xylene, etc.) and aliphatic hydrocarbons (petroleum ether, etc.).

[0037] The reaction temperature in the above production method is preferably 85 to 110°C, more preferably 90 to 105°C, and further preferably 95 to 100°C.

[0038] The reaction end point in the above production method varies depending on the reaction temperature, the amount of catalyst added, etc., and is not particularly limited, but can be, for example, the time when the remaining amount of the cyclic ester compound becomes less than 1% by weight as determined by analyzing the reaction solution by gas chromatography, etc. The reaction time is usually preferably 3 to 20 hours, more preferably 5 to 12 hours.

[0039] The above-mentioned production method can be carried out by putting the raw materials into a reaction vessel and heating them while stirring and mixing them. The raw materials can be mixed all at once before being put into the reaction vessel, or the hydroxyalkyl (meth)acrylate compound, the diaryl phosphate, etc. can be put into the reaction vessel, and then the cyclic ester compound can be added by dropping, etc.

[0040] The above production method can be carried out using a known reaction apparatus (such as a stirred tank type, a flow type such as a packed tower, or a fluidized bed type) in any system such as a batch system, a semi-batch system, or a continuous system.

[0041] According to the above-mentioned production method, it is possible to produce the above-mentioned lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product, in which the content of the di(meth)acrylate compound represented by the following formula (4) is preferably 0.4% by weight or less, more preferably 0.3% by weight or less, and even more preferably 0.2% by weight or less. [ka]

[0042] R in Equation (4) 1 and R 2 is R in the above formula (2). 1 and R 2 is the same as:

[0043] That is, the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product of the present disclosure contains preferably 0.4 wt % or less, more preferably 0.3 wt % or less, and even more preferably 0.2 wt % or less of the di(meth)acrylate compound represented by the above formula (4).

[0044] The lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product has a low content of the di(meth)acrylate compound, so that the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound in the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product as a monomer component is contained in the reactive oligomer, and the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound in the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product and / or the oligomer are contained in the curable resin composition as a monomer component, and the formation of three-dimensional crosslinks can be suppressed, and a significant increase in viscosity and gelation can be reduced. Therefore, the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product can be suitably used as a raw material for the reactive oligomer and the curable resin composition.

[0045] Examples of the reactive oligomer of the present disclosure include a urethane (meth)acrylate oligomer which is a reaction product of the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound in the above-mentioned lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product with a polyol compound and a polyisocyanate compound, and a (meth)acrylic polyol which is a reaction product of the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound in the above-mentioned lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product with a (meth)acryloyl group-containing compound.

[0046] The curable resin composition of the present disclosure can reduce a significant increase in viscosity and gelation, and can form a molded article with high uniformity, and is therefore suitable for use as, for example, a coating material.

[0047] The cured product of the curable resin composition of the present disclosure can be used, for example, as a cured coating film on a substrate. Examples of a coating method for coating the curable resin composition on a substrate include spray coating, brush coating, dip coating, roll coating, and flow coating.

[0048] The above-mentioned coated substrates are not particularly limited and may be used for applications such as construction materials (decorative panels, etc.), daily necessities (tableware, etc.), and electrical equipment parts (connectors, switches, distribution boards, insulators, etc.), and examples thereof include wood, metal, glass, cloth, plastic, foam, etc. The thickness of the cured coating film is preferably, for example, 10 to 80 μm.

[0049] The above-mentioned configurations and combinations thereof of the present disclosure are merely examples, and addition, omission, substitution, and modification of the configurations are possible as appropriate within the scope of the present disclosure. Furthermore, the present disclosure is not limited by the embodiments, but is limited only by the claims. EXAMPLES

[0050] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples in any way.

[0051] In the following, Examples 1 and 2 and Comparative Examples 1 and 2, examples relating to the production of lactone-modified hydroxyalkyl (meth)acrylic acid ester compounds will be shown.

[0052] The concentration of ε-caprolactone in the reaction liquid and the content of the di(meth)acrylate compound in the resulting lactone-modified hydroxyalkyl(meth)acrylic acid ester compound were measured by gas chromatography under the following conditions.

[0053] (Gas chromatography measurement conditions) Equipment: GC2014 (Shimadzu Corporation) Autosampler: AOC-20i+s (Shimadzu Corporation) Capillary column: HP-5MS (Agilent Technologies), column length 30 m, column inner diameter 0.25 mm, film thickness 0.25 μm Sample injection volume: 0.5μL ·Inlet temperature: 180℃ Detector temperature: 280℃ / FID Oven temperature: hold at 60°C (5 min), increase temperature (5°C / min), hold at 190°C (0 min), increase temperature (40°C / min), hold at 280°C (26.75 min) Split ratio: 50 Carrier gas: He gas, 1.0 ml / min, linear velocity control ·Quantitative method: Internal standard method Internal standard: Di-n-propyl succinate (98%, Alfa Aesar)

[0054] Example 1 4.3 mol (495.7 g) of 2-hydroxyethyl acrylate, 4.3 mol (504.4 g) of ε-caprolactone, 0.5 g of 4-methoxyphenol, and 0.2 g of diphenyl phosphate (DPP) (200 ppm by weight relative to the total amount of 2-hydroxyethyl acrylate and ε-caprolactone) were placed in a 1-liter five-neck flask equipped with a gas inlet tube, a stirrer, a cooling tube, and a temperature controller, and the mixture was stirred while being heated to 100°C in a 7% O2 atmosphere.

[0055] When the ε-caprolactone concentration became less than 1%, the reaction was stopped by cooling the reaction solution to obtain a lactone-modified hydroxyethyl acrylate. The content of the diacrylate compound was 0.17% by weight.

[0056] Example 2 Into a 1-liter five-neck flask equipped with a gas inlet tube, a stirrer, a cooling tube, and a temperature controller, 4.1 mol (467.2 g) of 2-hydroxyethyl methacrylate, 4.1 mol (532.8 g) of ε-caprolactone, 0.5 g of 4-methoxyphenol, and 0.2 g of diphenyl phosphate (DPP) (200 ppm by weight relative to the total amount of 2-hydroxyethyl methacrylate and ε-caprolactone) were added, and the mixture was stirred while being heated to 100°C in a 7% O2 atmosphere.

[0057] When the ε-caprolactone concentration became less than 1%, the reaction was stopped by cooling the reaction solution to obtain a lactone-modified hydroxyethyl methacrylate compound. The content of the dimethacrylate compound was 0.11% by weight.

[0058] Comparative Example 1 Into a 1-liter five-neck flask equipped with a gas inlet tube, a stirrer, a cooling tube, and a temperature controller, 4.3 mol (495.7 g) of 2-hydroxyethyl acrylate as an initiator, 4.3 mol (504.4 g) of ε-caprolactone as a cyclic ester, 5 g of 4-methoxyphenol, and 0.05 g of tin(II) chloride (50 ppm by weight with respect to the total amount of 2-hydroxyethyl acrylate and ε-caprolactone) were added, and the mixture was stirred while being heated to 115°C in a 7% O2 atmosphere.

[0059] When the ε-caprolactone concentration became less than 1%, the reaction was stopped by cooling the reaction solution to obtain a lactone-modified hydroxyethyl acrylate. The content of the diacrylate compound was 1.36% by weight.

[0060] Comparative Example 2 Into a 1-liter five-neck flask equipped with a gas inlet tube, a stirrer, a cooling tube, and a temperature controller, 4.1 mol (467.2 g) of 2-hydroxyethyl methacrylate as an initiator, 4.1 mol (532.8 g) of ε-caprolactone as a cyclic ester, 5 g of 4-methoxyphenol, and 0.05 g of tin(II) chloride (50 ppm by weight with respect to the total amount of 2-hydroxyethyl methacrylate and ε-caprolactone) were added, and the mixture was stirred while being heated to 115°C in a 7% O2 atmosphere.

[0061] When the ε-caprolactone concentration became less than 1%, the reaction was stopped by cooling the reaction liquid to obtain lactone polymer 4. The content of the dimethacrylate compound was 0.69% by weight.

[0062] As shown in Examples 1 and 2, the lactone-modified hydroxyethyl (meth)acrylic acid ester compounds produced using diphenyl phosphate had low dimethacrylate compound contents of 0.17% by weight and 0.11% by weight, respectively. On the other hand, the dimethacrylate compound contents of Comparative Examples 1 and 2, which used tin(II) chloride, were both high.

Claims

1. The following formula (2) 【Chemistry 4】 [In formula (2), R 1 represents hydrogen or a methyl group, and R 2 represents a linear alkylene group having 2 to 6 carbon atoms which may have a substituent] and a cyclic ester compound having 4 to 10 carbon atoms, 【Chemistry 1】 [In formula (1), Ar １ , Ar ２ Ar may be the same or different and represents an aryl group which may have a substituent. １ , Ar ２ may be bonded to each other to form a ring together with the (-O-P-O-) group. (excluding the case where the reaction is carried out in the presence of an organic acid bismuth salt), the amount of the diaryl phosphate added is 10 to 300 ppm by weight based on the total amount of the hydroxyalkyl (meth)acrylate compound and the cyclic ester compound; In the lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product, 【Chemistry 2】 [In formula (4), R 1 and R 2 are the same as those in formula (2)] The content of the di(meth)acrylate compound represented by the formula (I) is 0.4% by weight or less. A method for producing a lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product.

2. A method for producing a reactive oligomer, comprising obtaining a reactive oligomer containing, as a monomer component, a lactone-modified hydroxyalkyl (meth)acrylic acid ester compound in a lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product produced by the method according to claim 1.

3. A method for producing a curable resin composition, comprising obtaining a curable resin composition containing, as a monomer component, a lactone-modified hydroxyalkyl (meth)acrylic acid ester compound in a lactone-modified hydroxyalkyl (meth)acrylic acid ester compound product produced by the production method according to claim 1 and / or the reactive oligomer according to claim 2.

4. A method for producing a cured product, comprising forming a cured product from the curable resin composition obtained by the method according to claim 3.

Images