KR102255069B1 - Monoamine compound for emulsifier synthesis - Google Patents

Abstract

The present invention relates to a monoamine compound, and more particularly, to a monoamine compound for synthesizing an emulsifier. The monoamine compound according to the present invention can control the ratio of ethylene oxide and propylene oxide, and thus can be applied to various resins by synthesizing a multi-chain surfactant having physical properties suitable for the application through the monoamine compound of the present invention. The multi-chain surfactant can form micelles even at a lower concentration for application than single-chain surfactants or block copolymer surfactants, thereby exhibiting excellent emulsification performance and minimizing the amount of surfactant used in preparing aqueous epoxy.

Description

Monoamine compound for emulsifier synthesis {MONOAMINE COMPOUND FOR EMULSIFIER SYNTHESIS}

The present invention relates to a monoamine compound, and in particular, to a monoamine compound for synthesizing an emulsifier.

Recently, there is an increasing interest in eco-friendly products for health, environment and safety reasons. Since volatile substances used when manufacturing and utilizing synthetic resins not only destroy the natural environment but also adversely affect the human body, there is an urgent need for a technology that can replace them in an eco-friendly manner.

Epoxy resin has excellent inherent chemical resistance, water resistance, and abrasion resistance, so it is used as an inner wall, outer wall, or flooring material of buildings and civil structures. In particular, it gives color to the floor or prevents damage to the floor due to the movement of vehicles or pedestrians. It is a resin that is widely used for the purpose of preventing and preventing dust and the like from occurring from the floor.

However, since epoxy resins using organic solvents have odors and toxicity, it is difficult to work in an enclosed space, and there is a limitation in that it causes human health and environmental problems. Accordingly, to compensate for this, a water-based epoxy made of an epoxy resin was developed, and the scale of domestic and overseas related markets is steadily growing as it has high working stability and eco-friendly advantages because it does not use organic solvents harmful to the human body.

As a method for preparing an aqueous epoxy, there is a method of dispersing an epoxy resin through an emulsifier or introducing a hydrophilic substituent to the epoxy resin. In this regard, Korean Patent No. 10-1870910 proposes an eco-friendly water-soluble coating composition obtained by mixing a copolymer having a hydrophilic group and a silicone-based surfactant with an epoxy resin to make water-soluble, and Korean Patent No. 10-0938432 An ether glycol compound and a bisphenol epoxy compound are reacted to prepare an aqueous epoxy resin having excellent adhesion, gloss, and natural drying properties.

However, it is still a reality that commercially available water-based epoxy resins have insufficient physical properties required in the market to apply them to the field, and research and development for surfactants constituting the above water-based epoxy resins are insufficient. Accordingly, there is a need for development of a surfactant capable of exhibiting an excellent surfactant effect even at a low concentration and improving the physical properties of a coating film when forming a coating film, and a manufacturing method capable of producing the same in a high yield.

Korean Patent Registration No. 10-1870910 (registered on June 19, 2018) Korean Patent Publication No. 10-0938432 (registered on January 15, 2010)

The monoamine compound of the present invention has been devised to solve the above problems, and an object thereof is to provide a monoamine compound, which is a useful material that can be utilized in the production of a multi-chain emulsifier, and a method for preparing the same.

The present invention can also aim to achieve these objects and other objects that can be easily derived by a person skilled in the art from the general description of the present specification in addition to the above-described clear objects.

The monoamine compound of the present invention is characterized in that it is represented by the following formula (1) in order to achieve the object as described above.

[Formula 1]

R ¹ -(EO) _m (PO) _n -Z-NH ₂

In Formula 1,

R ¹ is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms,

The EO is ethylene oxide,

The PO is propylene oxide,

Wherein m and n are each an integer of 1 to 100,

Z may or may not be an optionally substituted hydrocarbyl or hydrocarbyloxy having 2 to 5 carbon atoms.

In addition, Z may have 3 to 4 carbon atoms, preferably 3 carbon atoms.

In addition, Z may be OCH ₂ CH(OH)CH ₂ .

In addition, R ¹ may be a methyl group, an ethyl group, a propyl group, or a butyl group.

In addition, the ratio of m and n may be 1:1 to 8:1, or 2:1 to 6:1, or 3:1 to 5:1.

In addition, the number average molecular weight of the monoamine compound may be 1000 to 6000, or 2000 to 5000, or 2600 to 4600.

On the other hand, the method for producing a monoamine compound of the present invention,

(A) reacting an alcohol compound represented by the ^{formula R 1} -(EO) _m (PO) _{n -OH with epichlorohydrin;} And

(B) reacting the product of step (A) with ammonia, wherein the monoamine compound is represented by the following formula (1).

[Formula 1]

R ¹ -(EO) _m (PO) _n -Z-NH ₂

R ¹ is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms,

The EO is ethylene oxide,

The PO is propylene oxide,

Wherein m and n are each an integer of 1 to 100,

Z may or may not be an optionally substituted hydrocarbyl or hydrocarbyloxy having 2 to 5 carbon atoms.

And, the step (A) can be reacted at 50 to 70 ℃ after creating a nitrogen atmosphere.

In addition, in the step (A), 1 mole part of the alcohol compound and 1 to 20 mole parts of epichlorohydrin, or 1 to 18 mole parts, or 1 to 12 mole parts may be mixed.

In addition, in the step (A), 1 mole part of the alcohol compound and 1 to 4 mole parts of epichlorohydrin, or 1.2 to 3 mole parts, or 1.8 to 2.2 mole parts may be mixed.

And, the step (A) may be reacted for 5 to 40 hours, or 12 to 36 hours, or 20 to 26 hours.

In the step (A), after the reaction, an excess of acetone is added, and the solvent is removed by rotary evaporation at 30 to 70°C or 40 to 60°C, followed by vacuum drying.

In addition, the step (A) may be carried out under basic conditions and reacted by adding tetrabutylammonium bromide (TBAB).

In addition, the tetrabutylammonium bromide may be mixed in an amount of 0.01 to 2 mole parts, or 0.1 to 1 mole parts, or 0.4 to 0.8 mole parts, based on 100 mole parts of the alcohol compound.

In addition, the step (A) may be reacted by adding boron trifluoride diethyl etherate.

In addition, after the reaction, NaOH may be added and stirred at 50 to 70° C. for 30 to 90 minutes, and then cooling may be further included.

In addition, the boron trifluoride ether may be mixed in an amount of 0.1 to 5 mole parts, or 0.4 to 2 mole parts, or 0.8 to 1.4 mole parts with respect to 100 mole parts of the alcohol compound.

And, in the step (B), after dissolving the compound produced in step (A) in a solvent, an aqueous ammonia solution is mixed at 80 to 160°C, or 90 to 120°C, or 95 to 110°C for 10 to 20 hours, Alternatively, it may be reacted by stirring for 12 to 18 hours, or 14 to 16 hours.

In addition, the step (B) may be reacted for 1 to 72 hours, 12 to 60 hours, 18 to 48 hours, or 20 to 36 hours by mixing the compound produced in the step (A) and an aqueous ammonia solution.

And, the step (B) may be carried out at 20 to 120 ℃, 40 to 100 ℃, or 50 to 80 ℃.

In addition, ethanol may be added to the glycidyl ether compound before mixing the compound produced in step (A) with the aqueous ammonia solution.

In addition, the ratio of m and n may be 1:1 to 8:1, or 2:1 to 6:1, or 3:1 to 5:1.

In addition, the manufacturing method of the monoamine compound may control the HLB of the monoamine compound by adjusting the ratio of m and n of the alcohol compound.

In addition, the alcohol compound ^{may be prepared by reacting R 1} OH with ethylene oxide and propylene oxide.

In addition, the step (B) may be reacted by mixing 1 part by weight of the product of step (A) and 10 to 25 parts by weight of the ammonia, preferably 14 to 20 parts by weight, more preferably 16 to 18 parts by weight. have.

The monoamine compound according to the present invention can adjust the ratio of ethylene oxide and propylene oxide, so that the monoamine compound of the present invention can synthesize a multi-chain type surfactant having properties suitable for use, and can be applied to various resins. Do.

The multi-chain surfactant prepared through the monoamine compound of the present invention can form micelles even at a lower application concentration than a single-chain surfactant or a block copolymer surfactant, so that excellent emulsification performance can be expressed. It is possible to minimize the amount of surfactant used.

In particular, the multi-chain surfactant or emulsifier is characterized to emulsify the epoxy resin, and the epoxy group remaining in the surfactant participates in the curing reaction, thereby preventing the problem of deteriorating the properties of the epoxy coating film due to elution of the surfactant.

1 is a structural formula of a multi-chain emulsifier synthesized using a monoamine compound according to an embodiment of the present invention.
2 is an NMR analysis result of an alcohol compound according to an embodiment of the present invention.
3 is an NMR analysis result of an alcohol compound according to an embodiment of the present invention.
4 is an NMR analysis result of an alcohol compound according to an embodiment of the present invention.
5 is an FT-IR analysis result of an alcohol compound according to an embodiment of the present invention.
6 is an NMR analysis result of glycidyl ether according to an embodiment and a comparative example of the present invention.
7 is an NMR analysis result of glycidyl ether according to an example and a comparative example of the present invention.

Hereinafter, a preferred embodiment of the present invention will be described in detail.

However, the following is only for describing in detail by exemplifying specific embodiments, and since the present invention may be variously changed and may have various forms, the present invention is not limited to the specific exemplary embodiments illustrated. It is to be understood that the present invention includes all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

In addition, in the following description, there are many specific details such as specific components, etc., which are provided to help a more general understanding of the present invention, and the present invention can be practiced without these specific details. It will be said that it is self-evident to those who have the knowledge of. Further, in describing the present invention, when it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted.

In addition, terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. Unless otherwise defined, all terms used herein including technical or scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms as defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted as an ideal or excessively formal meaning unless explicitly defined in the present application. Does not.

In this application, expressions in the singular include plural expressions unless the context clearly indicates otherwise.

In the present application, terms such as'include','include', or'have' are intended to refer to the presence of features, elements (or constituents), etc. described in the specification, but one or more other features or It does not mean that the component or the like does not exist or cannot be added.

Monoamine compounds

The monoamine compound of the present invention is characterized by represented by the following formula (1).

[Formula 1]

R ¹ -(EO) _m (PO) _n -Z-NH ₂

In Formula 1, R ¹ is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, EO is ethylene oxide, PO is propylene oxide, and m and n are each 1 to It is an integer of 100, and Z may or may not be an optionally substituted hydrocarbyl or hydrocarbyloxy having 2 to 5 carbon atoms.

In addition, R ¹ may be a methyl group, an ethyl group, a propyl group, or a butyl group, and preferably a methyl group.

In the present specification, hydrocarbyl means a carbon radical from which one or more hydrogen atoms have been removed, and hydrocarbyloxy means that oxygen is bonded to carbon constituting the hydrocarbyl group.

The Z may be a hydrocarbyl or hydrocarbyloxy substituted with a hydroxyl group having 2 to 5 carbon atoms, preferably 3 to 4, more preferably 3, and in particular, the Z may be OCH ₂ CH(OH)CH ₂ I can. In addition, Z may not be present, and in this case, the monoamine compound may be represented as R ¹ -(EO) _m (PO) _n -NH ₂ .

The monoamine of the present invention includes ethylene oxide (EO), and propylene oxide (PO), and is characterized in that they can be used as repeating units. The (EO) _m (PO) _n refers to a copolymer structure composed of EO and PO, and may be a random copolymer, a block copolymer, or an alternating copolymer. By controlling the ratio of EO and PO, a high-performance multi-chain emulsifier capable of controlling HLB (Hydrophilic-Lipophilic Balance) can be synthesized, and emulsifiers of various performances can be synthesized according to the ratio. Therefore, it is possible to easily prepare a suitable emulsifier according to the epoxy resin to be applied, and thus its utility is high.

That is, the monoamine compound of the present invention is a precursor of a multi-chain emulsifier, and a multi-chain emulsifier can be synthesized through a chemical reaction using the monoamine compound as a reactant. In particular, due to the structural characteristics of the monoamine compound of the present invention, an addition reaction that forms a link between the monoamine compounds through a bridge or a bond of an epoxy resin may be easily performed.

In the monoamine compound, the ratio of m and n, which is the ratio of EO and PO, may be 1:1 to 8:1, preferably 2:1 to 6:1, more preferably 3:1 to 5:1. Can be In order to stably emulsify the epoxy resin or maintain the dispersed state in a stable state without phase separation, precipitation or aggregation after emulsification and dispersion, it is very important to properly set the HLB of the monoamine compound. Here, HLB is determined according to the ratio of EO and PO. When the ratio of EO to PO is less than the above range, the monoamine compound is excessively hydrophobic, and when it exceeds the above range, the monoamine compound becomes excessively hydrophilic. It becomes difficult to secure dispersibility and storage stability of the prepared emulsion.

In addition, the number average molecular weight of the monoamine compound may be 1000 to 6000, or 2000 to 5000, or 2600 to 4600. If the average molecular weight is less than the above range, the emulsion stability may be deteriorated when emulsifying the solid epoxy resin, resulting in problems with storage properties such as precipitation, and water resistance may decrease when forming a coating film. On the other hand, if the average molecular weight exceeds the above range, the viscosity increases during emulsification, making it difficult to proceed with the emulsification process, and even after emulsification, it is difficult to uniformly mix the main material and the hardener due to the high viscosity, or the painting workability is deteriorated. Can occur.

On the other hand, the manufacturing method of the monoamine compound of the present invention, (A) ^{the alcohol compound represented by the formula R 1} -(EO) _m (PO) _n -OH tosyl chloride (Tosyl Chloride) or epichlorohydrin (Epichlorohydrin) and Reacting; And (B) reacting the product of step (A) with ammonia.

Since the monoamine compound of the present invention described above can be prepared by modifying the alcohol compound, the R ¹ , EO, PO, m, n are as defined above, and thus R ¹ is saturated with 1 to 10 carbon atoms or It is an unsaturated alkyl group, EO is ethylene oxide, PO is propylene oxide, and m and n may be integers of 1 to 100, respectively.

In addition, R ¹ may be a methyl group, an ethyl group, a propyl group, or a butyl group.

In addition, the ratio of m and n is 1:1 to 8:1, preferably 2:1 to 6:1, more preferably 3:1 to 5:1, even more preferably 3:1 to 4: May be 1.

In the method for preparing a monoamine compound of the present invention, the HLB of the monoamine compound may be adjusted by adjusting the ratio of m and n of the alcohol compound. More specifically, the alcohol compound may ^{be prepared by reacting R 1} OH with ethylene oxide and propylene oxide. At this time, a primary alcohol having an arbitrary HLB value may be synthesized by controlling the number of moles of EO and PO. The molecular weight of the EO/PO-controlled primary alcohol may be 1000 to 6000, or 2000 to 5000, or 2600 to 4600.

In order to synthesize a monoamine through an alcohol compound in which EO/PO is controlled, the hydroxyl group of the alcohol compound has a step (A) of introducing a functional group having excellent reactivity with ammonia. Step (A) may be performed through two methods, and tosyl chloride or epichlorohydrin may be used.

First, in the case of using a tosyl chloride, the step (A) includes 100 mole parts of the alcohol compound, 150 to 300 mole parts of tosyl chloride, preferably 150 to 250 mole parts, more preferably 180 to 220 mole parts, and 150 to 300 mole parts of pyridine. It may be a step of mixing, preferably 150 to 250 mole parts, more preferably 150 to 220 mole parts.

More specifically, 100 mol parts of the alcohol compound are added to a solvent such as DCM, stirred at 0° C., 150 to 300 mol parts of tosyl chloride are added, and 150 to 300 mol parts of pyridine are added to react. At this time, the reaction time is preferably 2 to 4 hours. After that, the product can be obtained through washing and purification processes.

The tosyl chloride may react with an alcohol compound to form a tosyl group in the alcohol compound. Thus, the intermediate product according to step (A) can be represented as ^{R 1} -(EO) _m (PO) _{n -OTs.}

On the other hand, in the case of using epichlorohydrin, the step (A) includes adding epichlorohydrin to the solution containing the alcohol compound and then adding sodium hydroxide, and then adding sodium hydroxide to the solution containing the alcohol compound. Injecting epichlorohydrin, or adding epichlorohydrin to a solution in which the alcohol compound, sodium hydroxide, quaternary ammonium salt, and hexane are mixed.

And, the step (A) can be reacted at 50 to 70 ℃ after creating a nitrogen atmosphere. In addition, in the step (A), 1 mole part of the alcohol compound and 1 to 4 mole parts of epichlorohydrin, or 1.2 to 3 mole parts, or 1.8 to 2.2 mole parts may be mixed. In addition, the step (A) may be reacted for 5 to 40 hours, or 12 to 36 hours, or 20 to 26 hours. In the step (A), after the reaction, an excess of acetone is added, and the solvent is removed by rotary evaporation at 30 to 70°C or 40 to 60°C, followed by vacuum drying.

In addition, the step (A) may be carried out under basic conditions and reacted by adding tetrabutylammonium bromide (TBAB). The tetrabutylammonium bromide may be mixed in an amount of 0.01 to 2 mole parts, or 0.1 to 1 mole parts, or 0.4 to 0.8 mole parts, based on 100 mole parts of the alcohol compound.

Meanwhile, the step (A) may be reacted by adding boron trifluoride diethyl etherate. In this case, the reaction may further include adding NaOH, stirring at 50 to 70° C. for 30 to 90 minutes, and cooling. In addition, the boron trifluoride ether may be mixed in an amount of 0.1 to 5 mole parts, or 0.4 to 2 mole parts, or 0.8 to 1.4 mole parts with respect to 100 mole parts of the alcohol compound.

After the step (A), the step (B) may be a reaction of introducing an amine group to the alcohol compound through ammonia, and specifically, 1 part by weight of the product of step (A) and 10 to 25 parts by weight of the ammonia, Preferably, 14 to 20 parts by weight, more preferably 16 to 18 parts by weight may be mixed and reacted.

Specifically, the step (B) is 80 to 160 °C, or 90 to 120 °C, or 95 to 110 °C by dissolving the glycidyl ether compound produced in step (A) in a solvent and then mixing an aqueous ammonia solution. In 10 to 20 hours, or 12 to 18 hours, or may be reacted by stirring for 14 to 16 hours. According to the manufacturing method of the monoamine compound according to the present invention, the yield can be remarkably improved, so that the economic efficiency and efficiency of the manufacturing process can be improved, and the technology commercialization is advantageous.

Another method for preparing a monoamine compound of the present invention includes the steps of: (A) reacting an alcohol compound represented by the ^{formula R 1} -(EO) _m (PO) _{n -OH with epichlorohydrin;} And (B) reacting the product of step (A) with ammonia; wherein step (A) includes 1 mole part of the alcohol compound and 1 to 20 mole parts of the epichlorohydrin, or 1 to 18 mole parts, Alternatively, it is characterized in that mixing 1 to 12 molar parts.

In addition, the step (B) is 1 to 72 hours, 12 to 60 hours, 18 at 20 to 120 °C, 40 to 100 °C, or 50 to 80 °C by mixing the compound produced in step (A) with an aqueous ammonia solution. To 48 hours, or 20 to 36 hours, the ammonia aqueous solution may be 20 to 40%, 24 to 36%, or 28 to 32%. Before mixing the aqueous ammonia solution with the compound produced in step (A), ethanol may be added to the compound produced in step (A). The compound produced in step (A) may be glycidyl ether or chloride.

When the ethanol is not added, the molar ratio of the glycidyl ether compound and the aqueous ammonia solution may be 1: 40 to 60, 1: 42 to 58, or 1: 48 to 53. On the other hand, when ethanol is first added, the ethanol input amount may be 10 to 40 mole parts, 12 to 30 mole parts, or 16 to 26 mole parts per 1 mole part of glycidyl ether, and the amount of the aqueous ammonia solution is 1 mole part of the glycidyl ether compound. It may be 8 to 20 mole parts, 10 to 18 mole parts, and 11 to 15 mole parts.

Multi-chain type surfactant

Meanwhile, a multi-chain type surfactant can be prepared through the monoamine compound of the present invention, and the method for preparing the multi-chain type surfactant (epoxy emulsifier) is (a) a monoamine compound represented by the following formula (1). Reacting a diglycidyl ether compound represented by the following formula (2); And (b) reacting the product of step (a) with an epoxy resin.

[Formula 1]

R ¹ -(EO) _m (PO) _n -Z-NH ₂

[Formula 2]

Since the above-described multi-chain epoxy emulsifier of the present invention can be prepared by modifying the monoamine compound, the R ¹ , EO, PO, m, and n are as defined above.

In the diglycidyl ether compound forming a bond with the monoamine compound, R'may _{be represented by (R''O)r} R'', and R'' is an alkyl having 1 to 4 carbon atoms. And, r may be an integer of 0 to 60, or 0 to 50, or 0 to 40. In particular, the diglycidyl ether may be polypropylene glycol diglycidyl ether (PPGDGE).

And, the number average molecular weight of the diglycidyl ether compound may be 100 to 1000, preferably 150 to 900, more preferably 200 to 800, the epoxy equivalent of 200 to 400 g/eq, or 300 to 360 It may be g/eq. When the number average molecular weight of the diglycidyl ether compound is less than the above range, it is difficult to apply a commercially available product. On the other hand, when the number average molecular weight of the diglycidyl ether compound is less than the above range, the ratio of the hydrophilic group in the emulsifier decreases, making it difficult to emulsify the epoxy resin. It is difficult to secure mechanical properties, such as lowering the hardness of the cured coating film.

First, in step (a), the monoamine compound and the diglycidyl ether compound are mixed to induce a reaction. At this time, the nitrogen of the amine provides electrons to the epoxide, thereby causing a ring opening reaction to form an NC bond. Can be formed. In addition, two reaction sites as described above are present per molecule of diglycidyl ether, reacting with two equivalents of a monoamine compound, resulting in a bridge between amines. In addition, the step (a) may be reacted by adding 0.01 to 0.1, preferably 0.02 to 0.06, more preferably 0.03 to 0.04 parts by weight of tributylamine based on 100 parts by weight of the monoamine compound.

The product produced through the step (a) may be referred to as a multi-chain emulsifier first-stage synthetic product, and the first-stage synthetic product may be represented by the following Chemical Formula 3, and is characterized in that it is a secondary amine.

[Formula 3]

In the step (a), specifically, 100 parts by weight of the monoamine compound, and 10 to 25 parts by weight of the diglycidyl ether compound, preferably 12 to 20 parts by weight, more preferably 14 to 18 parts by weight, are mixed. It may be to react.

Next, in step (b), the reaction is induced by mixing the synthetic product of step 1 and the epoxy resin, and similarly to step (a), the nitrogen of the amine provides electrons to the epoxide of the epoxy resin, resulting in a ring opening reaction. NC bonds can be formed. In addition, two reaction sites as described above exist per molecule of the first-stage synthetic product to react with two equivalents of the epoxy resin, and through this, the final product has a multi-chain structure. The multi-chain epoxy emulsifier produced through step (b) is characterized in that it is a tertiary amine. 1 shows the structure of a multi-chain type epoxy emulsifier according to an embodiment of the present invention.

The epoxy resin, which is the reactant of step (b), may be a Bisphenol A type, Bisphenol F type, Hydrogenated Bisphenol A type, or Novolac type epoxy resin. In addition, the equivalent weight of the epoxy resin may be 100 to 1200, preferably 150 to 1100, more preferably 170 to 1000. If the number average molecular weight of the epoxy resin is less than the above range, it is not commercially available, so it is difficult to separately synthesize it as a new compound.On the other hand, if the number average molecular weight of the epoxy resin is exceeded, it is difficult to handle and may cause a problem that the viscosity increases during the emulsification process. have.

The multi-chain surfactant prepared through the monoamine compound of the present invention can form micelles even at a lower application concentration than a single-chain surfactant or a block copolymer surfactant, thereby expressing excellent emulsifying performance and producing an aqueous epoxy. It is possible to minimize the amount of surfactant used. In particular, the HLB can be easily controlled and applied to various epoxy resins, and the epoxy group remaining in the surfactant participates in the curing reaction, thereby preventing the problem of deteriorating the properties of the epoxy coating film due to elution of the surfactant.

Hereinafter, an embodiment of the present invention will be described.

Example

Preparation Examples 1 to 6: Preparation of primary alcohol compound

Into a stainless steel autoclave equipped with a stirring device, a temperature control device, and an automatic introduction device, an alkali catalyst such as 1 mol alcohol and 0.5 to 1 mol% potassium hydroxide (KOH) was injected, and dehydration was performed at 110° C. and 1.3 kPa for 30 minutes. Implemented. After dehydration, nitrogen substitution was performed, the temperature was raised to 155° C., and then 3, 4, or 5 mol of ethylene oxide (EO) was injected. After completion of the injection, the reaction was carried out at 155°C for 30 minutes to obtain an ethylene oxide adduct having an average added mole number of 3, 4, or 5 moles, respectively. Then, after cooling the ethylene oxide adduct to 130° C., 1 mol of propylene oxide (PO) was injected. After completion of the injection, the reaction was carried out at 130° C. for 3 hours to obtain an alkylene oxide adduct (ethylene oxide and propylene oxide block adduct) having an average added mole number of 3, 4, or 5 moles of ethylene oxide and 1 mole of propylene oxide. According to the molar ratio of EO and PO, the primary alcohol compounds CH ₃ -(EO) _m (PO) _n -OH of Preparation Examples 1 to 6 were prepared as shown in Table 1 below.

EO:PO Manufacturing Example 1 3:1 Manufacturing Example 2 4:1 Manufacturing Example 3 5:1 Manufacturing Example 4 3:1 Manufacturing Example 5 4:1 Manufacturing Example 6 5:1

Test Example 1: Measurement of molecular weight of alcohol compound

The alcohol compounds prepared in Preparation Examples 1 to 6 were subjected to GPC analysis according to the following analysis conditions, and as a result, the molecular weight of each compound was shown in Table 2 below.

Column: Shodex GPC KF-805L

Eluent: THF

Flow rate: 1 ml/min

Detector: RI

Calibration: PS

Molecular Weight Manufacturing Example 1 3000 Manufacturing Example 2 2886 Manufacturing Example 3 2830 Manufacturing Example 4 4523 Manufacturing Example 5 4080 Manufacturing Example 6 3770

Test Example 2: NMR analysis of alcohol compounds

NMR analysis was performed on the alcohol compounds prepared in Preparation Examples 1 to 3, and the results are shown in FIGS. 2 to 4, respectively. Through this, it can be seen that the alcohol compound having the desired EO/PO molar ratio (3:1, 4:1, 5:1) in Preparation Examples 1 to 3 was well synthesized.

Test Example 3: FT-IR analysis of alcohol compounds

FT-IR analysis was performed on the alcohol compounds prepared in Preparation Examples 1 to 3, and the results are shown in FIG. 5. The functional groups corresponding to the observed peaks are shown in Table 3 below, and it can be seen that the target EO/PO primary alcohol compound was well synthesized.

Sample Wavenumbers (cm ^-One ) Assignments EO/PO
3:1
4:1
5:1 3444 OH stretching 2969, 2882, 2741, 2695 Stretching of aliphatic asymmetric and symmetric -CH ₂ -, -CH ₃ 1466 CH ₂ scissors vibration or CH ₃ antisymmetric deformation 1359 CH ₃ symmetric deformation 1342 COO ^- symmetric stretching 1279, 1241 Stretching of C-O or Stretching of C-O-C 1146, 1102, 1060 Stretching of C-OH
or Antisymmetric stretching of COC 961 CH ₂ out-of-plane wag 842 CH ₂ out-of-plane deformation

Example 1: Glycidyl ether synthesis (1)-TBAB catalyst addition

After creating a nitrogen atmosphere for 3Neck-RBF, 20 g (0.01 mol) of the alcohol compound prepared in Preparation Example 1 was added, and the temperature was raised to 60°C. After adding 0.02 g (0.0625 mmol) of the catalyst Tetrabutyl ammonium bromide (TBAB) and 1.24 g (0.015 mol) of 50 w/v% NaOH and stirring, 1.564 ml (0.02 mol) of Epichlorohydrin was added dropwise for 5 minutes for 24 hours (5, 12, 48 hours). After the reaction, an excessive amount of Acetone was added, and after treatment with a rotary evaporator at 50°C, the solvent was removed with a 50°C vacuum oven.

Comparative Example 1: Glycidyl ether synthesis (2)-TBAB catalyst not added

Glycidyl ether was synthesized in the same manner as in Example 1, but synthesized without adding catalyst TBAB.

Test Example 4: Comparison of yield with or without TBAB catalyst

NMR analysis was performed to evaluate the yield for Example 1 and Comparative Example 1, and the results are shown in FIGS. 6 and 7 and Table 4 below. 6 is an NMR graph according to reaction time for Example 1, and FIG. 7 is an NMR graph according to reaction time for Comparative Example 1. FIG. Through this, it was confirmed that as the reaction time increased, the yield increased regardless of the presence or absence of a catalyst, and the yield was higher in the presence of a catalyst. However, in the presence of a catalyst, a yield of about 40% was shown even at a reaction time of 24 h, but a yield of 31% was shown at a reaction time of 48 h in the absence of a catalyst, indicating that the reaction proceeds faster in the presence of a catalyst than in the absence of a catalyst.

Yield according to reaction time (%) Reaction time (h) 12 24 48 Example 1 31 40 41 Comparative Example 1 24 26 31

Example 2: Glycidyl ether synthesis (3)-BF ₃ Catalyst addition

After creating a nitrogen atmosphere inside the 3Neck-RBF, 20 g (0.01 mol) of the alcohol compound prepared in Preparation Example 1 was added, and the temperature was raised to 60°C. Catalyst Boron trifluoride ethyl etherate (BF ₃ etherate) 0.0142 g (0.1 mmol) was added and stirred, and 1.564 ml (0.02 mol) of Epichlorohydrin was dropwise for 5 minutes, followed by reaction for 24 hours and cooled to room temperature. Then, 1.635 g (0.02 mol) of 50 w/v% NaOH was added, the temperature was raised again to 60° C. for 1 hour, stirred, and then cooled. After adding an excessive amount of Acetone, a rotary evaporator was treated at 50°C, and the solvent was removed in a 50°C vacuum oven.

Comparative Example 2: Glycidyl ether synthesis (4)-BF ₃ No catalyst added

Glycidyl ether was synthesized in the same manner as in Example 2, but synthesized without adding _{catalyst BF 3.}

Test Example 5: BF ₃ Yield comparison with or without catalyst

In order to evaluate the yield of Example 2 and Comparative Example 2, NMR analysis was performed, and the yield was 121% when measured immediately after completion of the reaction, and 110% when measured after the reaction was terminated and treated with a rotary evaporator.

Example 3: Glycidyl ether synthesis (5)

Toluene 398.575 ml (3.75 mol), epichlorohydrin 39.1 ml (0.5 mol) was added to make a mixed solution, and 200 g (0.05 mol) of the alcohol compound prepared in Preparation Examples 1 to 6 were added thereto. I did. After confirming that all of the alcohol was dissolved, 20 g (0.5 mol) of NaOH powder was added, the temperature was raised to 60° C., and the mixture was reacted for 10 hours. At this time, after partial extraction for each reaction time, the degree of reaction was observed by NMR. After the reaction, the product was transferred to a separating funnel, 500 ml of deionization water (DW) was added, 10 ml of a saturated NaCl aqueous solution was added, and then physically shaken to mix fractions (repeated twice with DW). The obtained DW layer was extracted (repeated 3 times) using 750 ml of MC, and 30 g of sodium sulfate was added to the obtained MC (methyl chloride) layer, followed by stirring for 30 minutes to remove moisture. Then, sodium sulfate was removed by filtration under reduced pressure, and MC was removed by rotary evaporator treatment in a 50°C water bath. Cold diethyl ether was added to the obtained product for recrystallization, the supernatant was discarded, and the remaining solvent was removed by treatment with a rotary evaporator at room temperature. After that, it was dried in a vacuum oven at RT.

Example 4: Preparation of EO/PO monoamine compound (1)

30 ml (0.51 mol) of a 29% aqueous ammonia solution was added to 0.01 mol of the glycidyl ether prepared in Example 3, and the mixture was stirred for 24 hours. Then, after treatment with a rotary evaporator at 50°C, the solvent was removed in a 50°C vacuum oven to obtain an EO/PO monoamine compound.

Test Example 6: NMR analysis of EO/PO monoamine

¹ H-NMR and ¹³ C-NMR analysis were performed for each reaction time of the monoamine compound having EO:PO of 4:1 among the monoamine compounds prepared in Example 4, and the results are shown in FIGS. 8 and 9, respectively. . Through this, it was confirmed that the monoamine compound was well synthesized.

Example 5: Preparation of EO/PO monoamine compound (2)

10 g of ethanol was added to 0.01 mol of the glycidyl ether prepared in Example 3, and 7.3 ml (0.124 mol) of a 29% aqueous ammonia solution was added. Then, the temperature was raised to 60° C. and reacted for 24 hours. After treatment with a rotary evaporator at 50° C., the solvent was removed in a 50° C. vacuum oven to obtain an EO/PO monoamine compound.

Test Example 7: NMR analysis of EO/PO monoamine

¹ H-NMR and ¹³ C-NMR analysis were performed for each reaction time of the monoamine compound having EO:PO of 4:1 among the monoamine compounds prepared in Example 5, and the results are shown in FIGS. 10 and 11, respectively. . Through this, it was confirmed that the monoamine compound was well synthesized. In addition, it can be seen that when a monoamine compound is prepared according to Example 5, the synthesis time can be shortened by improving the reaction rate.

Example 6: Preparation of aqueous epoxy resin (1)

After adding 1000 g of EO/PO monoamine and 0.22 g of tributylamine prepared in Example 3 to a 2 L four-neck flask equipped with a thermometer, a condenser, and a stirrer, the temperature was gradually raised to 130° C. 104 g of propylene glycol diglycidyl ether (Kukdo Fine Chem DE-209, epoxy equivalent 320 g/eq)) was uniformly added dropwise for 3 hours and then maintained. After that, it was confirmed that the epoxy equivalent was 170,000 g/eq or more, and a first-stage synthetic product was obtained.

After adding 306 g of bisphenol A (Bisphenol A) epoxy resin (Kukdo Chemical YD-011, epoxy equivalent 475 g/eq) to the first-stage synthetic product, the reaction was terminated at the point where there was no change in epoxy equivalent, and a multi-chain epoxy emulsifier (average Molecular weight 8,000 to 9,000) was prepared.

Thereafter, 336 g of bisphenol A type epoxy resin (Kukdo Chemical YD-011, epoxy equivalent 475 g/eq) and 35 g of methoxy propanol were added to a 1-liter high-speed stirring device equipped with a thermometer, a condenser, and a stirrer. After the temperature was raised to 60° C. and completely dissolved, 49 g of the multi-chain type epoxy emulsifier was added and dissolved. While stirring at the same temperature at high speed, 280 g of ionized water was added dropwise for 4 hours to emulsify, thereby obtaining a water-soluble epoxy resin.

Comparative Example 3: Preparation of water-based epoxy resin (2)

After adding 350 g of bisphenol A type epoxy resin (Kukdo Chemical YD-011, epoxy equivalent 475 g/eq), 35 g of methoxy propanol to a 1-liter high-speed stirring device equipped with a thermometer, a condenser, and a stirrer, then 60 ℃ After the temperature was raised to and completely dissolved, 35 g of a single chain emulsifier (EO/PO BLOCK COPOLYMER, molecular weight of about 8000) was added and dissolved. While stirring at the same temperature at high speed, 280 g of ionized water was added dropwise for 4 hours to emulsify, thereby obtaining a water-soluble epoxy resin.

Test Example 8: Analysis of water-based epoxy properties

The average particle size, non-volatile content, epoxy equivalent, and viscosity of the aqueous epoxy prepared in Example 6 and Comparative Example 3 were measured, and the results are shown in Table 5 below.

Average particle size
(nm) Non-volatile matter
(%) Epoxy equivalent
(g/eq) Viscosity
(cps) Example 4 520 55.3 536 280 Comparative Example 3 660 55.7 522 1000

As shown in Table 5, it can be seen that the epoxy resin containing the multi-chain emulsifier prepared through the monoamine compound according to the present invention has a significantly lower viscosity than the conventional epoxy resin. Therefore, the monoamine compound according to the present invention can provide a multi-chain type emulsifier capable of producing a water-based epoxy resin that is easy to uniformly mix a main material and a curing agent and has excellent coating workability, so it will be widely used in related industries It is expected to be possible.

In the above, preferred embodiments of the present invention have been described, but the present invention is not limited to the specific embodiments described above, and those of ordinary skill in the art can implement various modifications without departing from the gist of the present invention. Of course it is possible. Therefore, the scope of the present invention should not be construed as limited to the above embodiments, and should be defined by the claims and equivalents as well as the claims to be described later.

Claims (11)

Monoamine compound for synthesizing a multi-chain emulsifier represented by the following formula (1):
[Formula 1]
R ¹ -(EO) _m (PO) _n -Z-NH ₂
In Formula 1,
R ¹ is a C 1 to C 10 saturated alkyl group or an unsaturated alkenyl group,
The EO is ethylene oxide,
The PO is propylene oxide,
M and n are each an integer of 1 to 100,
The ratio of m and n is 3:1 to 5:1,
Z may or may not be an optionally substituted hydrocarbyl or hydrocarbyloxy having 2 to 5 carbon atoms. delete The method according to claim 1,
A monoamine compound, characterized in that the number average molecular weight of the monoamine compound is 1000 to 6000. (A) reacting an alcohol compound represented by the ^{formula R 1} -(EO) _m (PO) _{n -OH with epichlorohydrin;} And
(B) reacting the product of step (A) with ammonia; wherein the monoamine compound is represented by the following formula (1),
The step (B) is characterized in that the compound produced in the step (A) is mixed with an aqueous ammonia solution and reacted for 1 to 72 hours,
Before mixing the compound produced in step (A) and the aqueous ammonia solution, ethanol is added to the compound produced in step (A), characterized in that:
[Formula 1]
R ¹ -(EO) _m (PO) _n -Z-NH ₂
In Formula 1,
R ¹ is a C 1 to C 10 saturated alkyl group or an unsaturated alkenyl group,
The EO is ethylene oxide,
The PO is propylene oxide,
Wherein m and n are each an integer of 1 to 100,
Z may or may not be an optionally substituted hydrocarbyl or hydrocarbyloxy having 2 to 5 carbon atoms. The method of claim 4,
The step (A) is characterized in that mixing 1 to 20 mole parts of the alcohol compound and 1 to 20 mole parts of the epichlorohydrin, a method for producing a monoamine compound. The method of claim 4,
Step (A) is carried out under basic conditions, characterized in that the reaction by adding tetrabutylammonium bromide (TBAB), a method for producing a monoamine compound. The method of claim 4,
The step (A), characterized in that the reaction by adding boron trifluoride diethyl etherate (Boron trifluoride diethyl etherate), a method for producing a monoamine compound. delete delete The method of claim 4,
The method for producing a monoamine compound, characterized in that the ratio of m and n is 1:1 to 8:1. The method of claim 4,
The method for producing a monoamine compound, characterized in that it is possible to control the HLB of the monoamine compound by adjusting the ratio of m and n of the alcohol compound.

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