KR102542899B1 - Novel n-sulfonyl aziridine compounds and its preparation method - Google Patents

Abstract

The present invention relates to a novel N-sulfonyl aziridine compound and a method for preparing the same, and more particularly, to an N-sulfonyl aziridine compound having an acrylate group to allow introduction of a double bond into an acrylic acid type pressure-sensitive adhesive and a method for preparing the same It is about.

Description

Novel N-sulfonyl aziridine compound and its preparation method {NOVEL N-SULFONYL AZIRIDINE COMPOUNDS AND ITS PREPARATION METHOD}

The present invention relates to a novel N-sulfonyl aziridine compound and a method for preparing the same, and more particularly, to an N-sulfonyl aziridine compound having an acrylate group to allow introduction of a double bond into an acrylic acid type pressure-sensitive adhesive and a method for preparing the same It is about.

Adhesion means a property that can form bonding strength immediately upon contact under a low pressure condition, and represents temporary adhesion to permanent adhesion. An adhesive having such characteristics is also called a pressure sensitive adhesive (PSA) in the sense that it adheres to an adherend by a small pressure in a short time at room temperature without using water, solvent, or heat. The adhesive initially has semi-solid properties intermediate between solid and liquid, and continues to maintain the same semi-solid properties after curing.

In general, acrylic adhesives are used throughout electrical and electronic, construction, automobile, ship, and medical industries. Acrylic adhesive is an acrylic acid ester-based copolymer that is colorless and transparent, does not yellow when exposed to sunlight, has excellent oxidation resistance, and has excellent weather resistance, oil resistance, and heat resistance. there is. In addition, because of its low price and relatively simple manufacturing process, it is currently widely used throughout the industry in special label paper or tape, adhesive sheet for surface protection, adhesive tape for masking, and dicing tape for wafer manufacturing process.

However, most acrylic adhesives use a crosslinking agent in a polymer obtained by copolymerizing a (meth)acrylate monomer and a monomer having a functional group on the side chain, so a mixing process of the adhesive and the crosslinking agent is required, and after mixing, the use time (pot life) Life)) is limited, and since the time required for perfect curing (aging time) is essential even after coating on the film, there is a disadvantage in that productivity is lowered. In particular, various heat-curing products are proposed to reduce aging time, which is directly related to productivity.

In order to compensate for this disadvantage, research to use a curing method by UV has been attempted.

For example, by copolymerizing a monomer having a carboxyl group and a hydroxyl group on the side chain of an acrylic polymer, glycidyl methacrylate (GMA) is reacted with the carboxyl group and isocyanoethyl (meth)acrylate is reacted with the hydroxyl group to form a photopolymerizable site. A manufacturing method, a method of adding a functional group such as a hydroxyl group to the main chain of the adhesive, followed by a secondary reaction with a compound having an isocyanate terminal, a silane or a compound having a glycidyl terminal terminal, and the like are known. However, the above technologies have problems in that a high reaction temperature of 60° C. or more is required when the acrylic copolymer and the photopolymerizable group-containing compound are reacted, or the use of a tin-based catalyst that causes toxicity is required.

Therefore, cross-linking by chemical reaction is possible during UV irradiation, so durability and adhesive properties can be realized only by UV irradiation without a separate cross-linking agent using an organic catalyst such as triethylamine at a low temperature of less than 50 ° C, preferably room temperature. There is a need to develop a new UV curable monomer capable of introducing a double bond into a structured UV curable monomer and an acrylic acid-based pressure-sensitive adhesive, that is, a new UV curable monomer capable of smoothly reacting with a carboxyl group of acrylic acid.

KR 10-2008-0062642 A KR 10-2010-0003717 A KR 10-2010-0008748 A

An object of the present invention is to provide an N-sulfonyl aziridine compound having an acrylate group and a method for preparing the same so that a double bond can be introduced into an acrylic acid type pressure-sensitive adhesive.

The present invention provides an N-sulfonyl aziridine compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

R is C1-C10 alkyl;

L is C1-C10 alkylene, and the alkylene of L may be further substituted with C1-C10 alkyl;

R ₁ and R ₂ are each independently hydrogen or C1-C10 alkyl;

m is an integer of 0, 1 or 2;

In addition, the present invention is a method for preparing the N-sulfonyl aziridine compound of Formula 1, comprising the steps of preparing a sulfonyl halide compound of Formula C by reacting a sulfonyl alkali metal salt of Formula A with an acid halogenating agent; and preparing an N-sulfonyl aziridine compound represented by Formula 1 by reacting a sulfonyl halide compound of Formula C with an aziridine compound of Formula D. to provide:

[Formula A]

[Formula C]

[Formula D]

In Formulas A, C and D, R ₁ , R ₂ , L, R and m are as defined in Formula 1 above;

M is an alkali metal;

X ₁ is halogen.

Since the novel N-sulfonyl aziridine compound according to the present invention has an acrylate group in the molecule and can introduce a double bond into an acrylic acid-type pressure-sensitive adhesive, it is a novel crosslinkable monomer capable of introducing a double bond into a dissociable acrylic acid-based pressure-sensitive adhesive. can be applied as

In particular, in contrast to the use of GMA (glycidyl methylmethacrylate) monomer, which is one of the universal methods for imparting double bond characteristics to adhesives, the N-sulfonyl aziridine compound having an acrylate group according to the present invention is a monomer for introducing a double bond When applied as a process, there is an advantage in that relatively low-temperature aging is possible.

Therefore, the novel N-sulfonyl aziridine compound according to the present invention is a novel monomer for introducing a double bond, and can be easily applied to the field of disintegrating acrylic acid-based pressure-sensitive adhesives in the future.

Figure 1 - ¹ H NMR spectrum of compound SPMA-Maz (Example 1)

Hereinafter, the present invention will be described in detail.

At this time, unless there is another definition in the technical terms and scientific terms used, they have meanings commonly understood by those of ordinary skill in the art to which this invention belongs. In addition, repeated description of the same technical configuration and operation as in the prior art will be omitted.

In this specification, the term “C _A -C _B ” means “a number of carbon atoms greater than or equal to A and less than or equal to B”.

The term “alkyl” in this specification means a monovalent straight-chain or branched saturated hydrocarbon radical composed only of carbon and hydrogen atoms. The alkyl may have 1 to 10 carbon atoms. The alkyl may have 1 to 7 carbon atoms. The alkyl may have 1 to 4 carbon atoms. Examples of such alkyl radicals include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, and the like.

The term “halogen” in this specification refers to a halogen group element and includes, for example, fluoro, chloro, bromo and iodo.

The term "alkylene" as used herein refers to a linear or branched saturated divalent hydrocarbon radical. The alkylene may have 1 to 10 carbon atoms. The alkylene may have 2 to 5 carbon atoms. Examples of such alkylene radicals include, but are not limited to, methylene, ethylene, propylene, and the like.

The present invention relates to a novel N-sulfonyl aziridine compound and a method for preparing the same, and more particularly, to an N-sulfonyl aziridine compound having an acrylate group to allow introduction of a double bond into an acrylic acid type pressure-sensitive adhesive and a method for preparing the same It is about.

The present invention provides an N-sulfonyl aziridine compound represented by Formula 1 below:

[Formula 1]

In Formula 1,

R is C1-C10 alkyl;

L is C1-C10 alkylene, and the alkylene of L may be further substituted with C1-C10 alkyl;

R ₁ and R ₂ are each independently hydrogen or C1-C10 alkyl;

m is an integer of 0, 1 or 2;

The N-sulfonyl aziridine compound according to the present invention has an acrylate group in the molecule and can be applied as a new crosslinkable monomer capable of introducing a double bond into an acrylic acid-based pressure-sensitive adhesive.

In particular, when the N-sulfonyl aziridine compound having an acrylate group according to the present invention is applied as a monomer for introducing a double bond, compared to the GMA (glycidyl methylmethacrylate) monomer used to impart the characteristics of a double bond to an adhesive, relatively Low-temperature reaction is possible, and it can be easily applied as a new monomer for introducing double bonds in the field of detachable adhesives that can be peeled off from substrates without residue by lowering adhesiveness after UV irradiation, such as dicing tapes for semiconductors in the future.

In one embodiment, when m is 2, R's may be the same as or different from each other.

In one embodiment, R is C1-C4 alkyl; L is C2-C5 alkylene, and the alkylene of L may be further substituted with C1-C4 alkyl; R ₁ and R ₂ are each independently hydrogen or C1-C4 alkyl; m may be an integer of 0, 1 or 2.

In one embodiment, L may be C2-C4 alkylene, preferably propylene.

In one embodiment, the N-sulfonyl aziridine compound may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

R is C1-C3 alkyl;

R ₁ is hydrogen or C1-C3 alkyl;

m is an integer of 0, 1 or 2;

In one embodiment, preferably, the N-sulfonyl aziridine compound may be represented by Formula 3 below.

[Formula 3]

In Formula 3, R is methyl or ethyl; R ₁ is hydrogen, methyl or ethyl.

In one embodiment, R is methyl; R ₁ can be hydrogen or methyl.

In addition, the present invention comprises the steps of preparing a sulfonyl halide compound of formula C by reacting a sulfonyl alkali metal salt of formula A with an acid halogenating agent; and

A method for preparing an N-sulfonyl aziridine compound comprising the steps of preparing an N-sulfonyl aziridine compound represented by Formula 1 by reacting a sulfonyl halide compound of Formula C with an aziridine compound of Formula D do:

[Formula A]

[Formula C]

[Formula D]

In Formulas A, C and D above,

R ₁ and R ₂ are each independently hydrogen or C1-C10 alkyl;

L is C1-C10 alkylene, and the alkylene of L may be further substituted with C1-C10 alkyl;

M is an alkali metal;

X ₁ is halogen;

R is C1-C10 alkyl;

m is an integer of 0, 1 or 2;

According to the production method of the present invention, a sulfonyl halide compound (Formula C) is prepared through the reaction of a sulfonyl alkali metal salt (Formula A) with an acid halogenating agent, followed by amidation with an aziridine compound (Formula D). ), it is possible to efficiently prepare an N-sulfonyl aziridine compound (Formula 1) having a desired acrylate group.

In one embodiment, the sulfonyl alkali metal salt of Formula A may be a sodium or potassium salt.

In one embodiment, the acid halogenating agent may be an oxalyl halide of Formula B below.

[Formula B]

In Formula B, X ₁ is halogen.

In one embodiment, the acid halogenating agent may be an acid chloride forming reagent, preferably oxalyl chloride.

The acid halogenating agent may be used in the same amount or in excess compared to the amount of the sulfonyl alkali metal salt of Formula A, specifically, 1 to 5 equivalents, preferably 1 to 3 equivalents, based on 1 equivalent of the sulfonyl alkali metal salt of Formula A. can be used as

In one embodiment, the reaction of the sulfonyl alkali metal salt of Chemical Formula A with the acid halide may be performed in the presence of a catalyst that promotes acid halide formation. Specific examples include dimethylformamide (DMF) and N-methylpyrrolidone (NMP), and dimethylformamide (DMF) is preferably used. The catalyst may be used in the range of 0.001 to 0.01 equivalents, preferably 0.003 to 0.005 equivalents, based on 1 equivalent of the sulfonyl alkali metal salt of Formula A, but is not limited thereto, and is adjusted within an appropriate range to exert the desired catalytic effect. and can be used.

In one embodiment, the reaction of the sulfonyl alkali metal salt of Formula A with the acid halogenating agent may be carried out at a temperature between -30 and 50 °C, more preferably between 0 and 25 °C.

The sulfonyl halide compound of Formula C prepared by the reaction of the sulfonyl alkali metal salt of Formula A with an acid halogenating agent is used in the next reaction without separation and purification.

In one embodiment, the aziridine compound of Formula D may be used in an amount of 1 to 3, preferably 1 to 1.5 equivalents based on 1 equivalent of the sulfonyl alkali metal salt compound of Formula A.

In one embodiment, the reaction with the aziridine compound of Formula D may be carried out in the presence of a base catalyst, and examples of the base catalyst that may be used include triethylamine. The base catalyst may be used in an amount of 1 to 4, preferably 1.5 to 2.5 equivalents based on 1 equivalent of the sulfonyl alkali metal salt compound of Formula A.

In one embodiment, the reaction with the aziridine compound of Formula D may be carried out at a temperature between -30 and -10°C, more preferably between -25 and -20°C.

In one embodiment, all of the above reactions may be performed in an organic solvent. There is no need to limit the organic solvent as long as it can dissolve the reactants participating in the reaction. Specifically usable organic solvents include dichloromethane (DCM), dichloroethane (DCE), 1,4-dioxane, tetrahydrofuran (THF), t-butyl alcohol, t-amyl alcohol, trifluoroethanol, xylene, Hexafluoroisopropanol, acetonitrile (MeCN), chlorobenzene, toluene, dimethylformamide (DMF), nitromethane, chloroform, etc., but not limited to, tetrahydrofuran (THF) in terms of more improved reactivity good to use

The reaction time may vary depending on the type and amount of the reactant, solvent, and the reaction is completed after the starting material is consumed and the product is confirmed through TLC or the like. When the reaction is completed, the target product may be separated and purified through a conventional method.

Hereinafter, the configuration of the present invention will be described in more detail through examples, but the following examples are intended to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

[Example 1] Preparation of 3-sulfopropylmethacrylate methylaziridine (compound SPMA-Maz)

Preparation of sulfonyl halide compound (C1)

After putting 10.0 g of 3-sulfopropyl methacrylate potassium salt (A1, sigma aldrich) and 30 ml of THF in a 250ml round flask, the mixture was stirred at 0° C. for 15 minutes. After slowly injecting 12.3 g of oxalyl chloride (B1), 3 to 4 drops of DMF as a catalyst were added, followed by stirring at 25°C for 3 hours. The precipitated salt was removed through filtration, and the filtrate containing the sulfonyl halide compound (C1) was directly used in the next reaction without separate purification.

Preparation of 3-sulfopropylmethacrylate methylaziridine (compound SPMA-Maz)

After putting 3.00 g of 2-methylaziridine (D1), 8.50 g of TEA, and 30 ml of THF in a 250 ml three-necked round flask, the mixture was stirred at -20 ° C for 15 minutes. A solution containing the previously obtained sulfonyl halide compound (C1) was slowly added dropwise through a dropping funnel over 60 minutes and then stirred at the same temperature for 1 hour. Then, the salt in the reaction solution was filtered through filtration, and the filtrate was fractionated and extracted using water and ethyl acetate, dried using MgSO ₄ , and then the solvent was removed from the collected organic layer in vacuo to obtain the target compound, 3-sulfopropylmethacrylate methylaziridine ( Compound SPMA-Maz) was obtained in the form of a colorless liquid. (yield 6.4 g, yield 64%) [Fig. 1].

¹ H NMR (300 MHz, 298 K, CDCl ₃ ): δ 6.13 (1H), 5.62 (1H), 4.32 (2H), 3.25 (2H), 2.83 (1H), 2.64 (1H), 2.33 (2H), 1.97 (3H), 1.35 (3H).

¹³ C NMR (75 MHz, 298 K, CDCl ₃ ): δ 167.18, 136.09, 126.11, 62.47, 49.65, 35.39, 34.41, 23.23, 18.42, 17.04.

HRMS (MALDI-TOF, m/z ): Calcd. for [M] = C ₁₀ H ₁₇ NO ₄ S; [M+H] ⁺ : 248.096, Found; [M+H] ⁺ : 248.117, [M+Na] ⁺ : 270.093.

[Example 2] Preparation of 3-sulfopropylacrylate methylaziridine (compound SPA-Maz)

Same method as Example 1 except for using 10.0 g of 3-sulfopropyl acrylate potassium salt (A2, sigma aldrich) instead of 3-sulfopropyl methacrylate potassium salt (A1) to obtain the target compound, 3-sulfopropylacrylate methylaziridine (compound SPA-Maz) in the form of a colorless liquid (yield: 5.9 g, yield: 59%).

¹ H NMR (300 MHz, 298 K, CDCl ₃ ): δ 6.43 (1H), 6.13 (1H), 5.87 (1H), 4.32 (2H), 3.23 (2H), 2.81 (1H), 2.63 (1H), 2.30 (2H), 2.07 (1H), 1.33 (3H).

¹³ C NMR (75 MHz, 298 K, CDCl ₃ ): δ 165.99, 131.50, 128.11, 62.32, 49.59, 35.40, 34.43, 23.19, 17.05.

HRMS (MALDI-TOF, m/z ): Calcd. for [M] = C ₉ H ₁₅ NO ₄ S; [M+H] ⁺ : 234.080, Found: [M+H] ⁺ : 234.062, [M+Na] ⁺ : 256.075.

Claims (6)

An N-sulfonyl aziridine compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
R is C1-C10 alkyl;
L is C1-C10 alkylene, and the alkylene of L may be further substituted with C1-C10 alkyl;
R ₁ and R ₂ are each independently hydrogen or C1-C10 alkyl;
m is an integer of 0, 1 or 2; According to claim 1,
wherein R is C1-C4 alkyl;
L is C2-C5 alkylene, and the alkylene of L may be further substituted with C1-C4 alkyl;
R ₁ and R ₂ are each independently hydrogen or C1-C4 alkyl;
m is an integer of 0, 1 or 2, N-sulfonyl aziridine compounds. According to claim 1,
The N-sulfonyl aziridine compound is an N-sulfonyl aziridine compound represented by Formula 2 below:
[Formula 2]

In Formula 2,
R is C1-C3 alkyl;
R ₁ is hydrogen or C1-C3 alkyl;
m is an integer of 0, 1 or 2; According to claim 1,
The N-sulfonyl aziridine compound is an N-sulfonyl aziridine compound represented by Formula 3 below:
[Formula 3]

In Formula 3, R is methyl or ethyl; R ₁ is hydrogen, methyl or ethyl. Preparing a sulfonyl halide compound of Formula C by reacting a sulfonyl alkali metal salt of Formula A with an acid halogenating agent; and
Preparing an N-sulfonyl aziridine compound represented by Formula 1 by reacting a sulfonyl halide compound of Formula C with an aziridine compound of Formula D;
[Formula 1]

[Formula A]

[Formula C]

[Formula D]

In Formula 1, A, C and D,
R ₁ and R ₂ are each independently hydrogen or C1-C10 alkyl;
L is C1-C10 alkylene, and the alkylene of L may be further substituted with C1-C10 alkyl;
M is an alkali metal;
X ₁ is halogen;
R is C1-C10 alkyl;
m is an integer of 0, 1 or 2; According to claim 5,
Wherein the acid halide is an oxalyl halide of Formula B.
[Formula B]

In Formula B, X ₁ is halogen.

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