WO2019033982A1 - Oxetane compound and preparation method therefor - Google Patents

Abstract

Disclosed is an oxetane compound used in a cation photocurable system. The oxetane compound is formed by a nucleophilic substitution reaction of a compound containing at least one hydroxyl and at least one oxetane group with a halohydrocarbon, and same is not sensitive to humidity, and has advantages such as a high reactive activity, low odor and viscosity, and strong adhesion.

Description

Oxetane compound and preparation method thereof Technical field

The invention belongs to the field of organic chemistry, and particularly relates to an oxetane compound which can be used in the field of photocuring and a preparation method thereof.

Background technique

The cationic photocuring system is not affected by oxygen inhibition, has a small shrinkage volume, and has good adhesion to plastic or metal substrates. Generally, a cationic photocuring system comprising an alicyclic epoxy compound, in contact with light of a suitable wavelength, is polymerized in the presence of a suitable photoinitiator to form a cured product having good heat resistance, adhesion and chemical resistance. . However, the application of alicyclic epoxy compounds has limitations, which are highlighted by sensitivity to humidity, and water vapor in the application environment can significantly reduce the curing speed. W. Watt summarizes the UV curing of epoxides in Chemistry & Technology of UV Curing, Vol. 2, pp 247-282, 1980, indicating that water promotes the termination of cationic polymerization, and thus high humidity significantly extends the UV curable epoxy coating. The time it takes for the layer to become non-sticky.

Recently, introduction of an oxetane compound into a cationic curing system has become a development trend, and is considered to be advantageous for the performance of a cured product, and progress has been made in the field of coating compositions and the like. However, the types of oxetane compounds in these coating compositions are limited, the selectivity is small, there is still a problem of sensitivity to humidity, and the cured product has an odor. Moreover, for solventless systems, the viscosity of these compositions is generally high, thereby limiting their use in some areas such as low viscosity inks.

In practical applications, oxetane compounds with improved performance, especially oxetane compounds which have high reactivity, are not sensitive to humidity, low viscosity, low or odorless, have been continuously pursued.

Summary of the invention

In view of the deficiencies of the prior art, the object of the present invention is mainly to provide a novel oxetane compound which is applied to a cationic photocuring system, which is insensitive to humidity, has high reactivity, low odor and viscosity, and adhesion. Strong and other advantages, is a reactive diluent with excellent performance.

The oxetane compound of the present invention is obtained by nucleophilic substitution reaction of a compound containing at least one hydroxyl group and at least one oxetane group with a halogenated hydrocarbon.

The above-mentioned compound containing at least one hydroxyl group and at least one oxetane group is a compound of the formula (I) disclosed in Chinese Patent Application No. 201610548580.7, or a patent disclosed in Chinese Patent Application No. a compound of formula (I). The entire contents of the two prior patent applications are hereby incorporated by reference. Herein, for the sake of distinction, the compounds of the two prior patent applications are each labeled as a compound of formula (I) and (II).

The halogenated hydrocarbon may be monohalogenated or polyhalogenated.

Specifically, the oxetane compound of the present invention is in the presence of a catalyst from a compound having a structure represented by the following formula (I) or (II) and a halogenated hydrocarbon having a structure represented by the formula (III). It is formed by nucleophilic substitution reaction:

In the general formula (I),

R ₁ represents a linear or branched a-valent alkyl group of C ₁ -C ₄₀ , an a-valent alkenyl group of C ₂ -C ₂₀ , a a-valent aryl group of C ₆ -C ₄₀ , wherein -CH ₂ - Optionally by -O-, -NH- or

Substituted, provided that the two -O- are not directly linked; and optionally, one or more of the hydrogen atoms of these groups may be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group;

R ₂ represents a C ₁ -C ₂₀ linear or branched alkylene group, and -CH ₂ - in the main chain may be optionally substituted by -O-, provided that two -O- are not directly linked, and Optionally, one or more hydrogen atoms in the group may each be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group;

R ₃ represents hydrogen, halogen, nitro, C ₁ -C ₂₀ linear or branched alkyl, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ cycloalkylalkyl, C ₄ -C An alkylcycloalkyl group of ₂₀ , an alkenyl group of C ₂ -C ₁₀ , an aryl group of C ₆ -C ₂₀ , optionally, one or more hydrogen atoms of these groups may each independently be selected from an alkane Substituted by a group of a halogen, a nitro group;

a represents an integer from 1 to 8;

In the general formula (II),

R ₄ means from

a b-valent organic residue obtained by removing b oxirane group structures, a linear or branched b-valent alkyl group selected from C ₁ -C ₄₀ , and a b-valent alkenyl group of C ₂ -C ₄₀ a B-valent cycloalkyl group of C ₃ -C _{40 ,} a b-valent cycloalkylalkyl group of C ₄ -C _{40 ,} a b-valent alkylcycloalkyl group of C ₄ -C _{40 , and} a b-valent aromatic group of C ₆ -C ₄₀ a C ₇ -C ₄₀ b-valent arylalkyl group,

Wherein -CH ₂ - may be optionally substituted by -O- or -OCH ₂ CH ₂ - provided that the two -O- are not directly attached;

R ₇ and R _{8 are the} same or different and each independently represents a C ₁ -C ₁₀ linear or branched alkylene group;

A ₁ and A _{2 are the} same or different and each independently represents an empty, C ₁ -C ₁₀ alkylene group or a phenylene group;

m ₁ and m ₂ represent 0 or an integer greater than 0;

B represents -CH ₂ -, -(CH ₂ -CH ₂ -O) _m -CH ₂ -, -[CH ₂ -CH(CH ₃ )-O] _m -CH ₂ -, wherein m represents 0 or greater than 0 Integer

R ₅ represents hydrogen, halogen, nitro, C ₁ -C ₂₀ linear or branched alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ a cycloalkylalkyl group, a C ₄ -C ₂₀ alkylcycloalkyl group, a C ₆ -C ₂₀ aryl group, optionally, one or more of the hydrogen atoms of these groups may be independently selected from the group consisting of alkane Substituted by a group of a halogen, a nitro group;

b represents an integer from 1-8;

In the general formula (III),

R ₆ represents a linear or branched c-valent alkyl group of C ₁ -C ₄₀ , a c-valent alkenyl group of C ₂ -C _{20 ,} a c-valent cycloalkyl group of C ₃ -C ₂₀ , or a C ₄ -C ₂₀ a c-valent cycloalkylalkyl group, a C ₄ -C ₂₀ c-valent alkylcycloalkyl group, a C ₆ -C ₄₀ c-valent aryl group, a C ₇ -C ₄₀ c-valent arylalkyl group, a C ₂ -C a c-valent heterocyclic group of ₁₀ , wherein -CH ₂ - may be optionally substituted by -O-, -S-;

X represents a halogen such as fluorine, chlorine, bromine or iodine;

c represents an integer from 1-8.

In a preferred embodiment, in the formula (I), R ₁ represents a C ₁ - C ₂₀ linear or branched a-valent alkyl group, a C ₂ - C ₁₀ linear or branched a-valent alkenyl group, a _6- valent aryl group of C ₆ -C ₃₀ wherein -CH 2 - may be optionally -O-, -NH- or

Substituted, provided that the two -O- are not directly linked; and optionally, one or more of the hydrogen atoms of these groups may be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group.

Further preferably, R ₁ represents a linear or branched a-valent alkyl group of C ₁ -C _{12 ,} a linear or branched a-valent alkenyl group of C ₂ -C ₈ , and a valence of C ₆ -C ₃₀ An aryl group, wherein -CH ₂ - may be optionally -O-, -NH- or

Substituted, the condition is that two -O- are not directly connected.

Illustratively, R ₁ may be selected from the following structures:

a straight or branched 1-4 valent alkyl group of C ₁ -C _{12 ,} a linear or branched 1-4 valent alkenyl group of C ₂ -C ₆ ,

CH ₃ -O-CH ₂ CH ₂ *,

*CH ₂ CH ₂ NHCH ₂ CH ₂ *,

Preferably, R ₂ represents a C ₁ -C ₁₀ linear or branched alkylene group, and -CH ₂ - in the main chain may be optionally substituted by -O-, provided that the two -O- are not directly Connected. Further preferably, R ₂ represents a C ₁ -C ₆ linear or branched alkylene group, and -CH ₂ - in the main chain may be optionally substituted by -O-, provided that two -O- Directly connected.

Preferably, R ₃ represents hydrogen, C ₁ -C ₁₀ linear or branched alkyl, C ₃ -C ₁₀ cycloalkyl, C ₄ -C ₁₀ cycloalkylalkyl, C ₄ -C ₁₀ Alkylcycloalkyl, C ₂ -C ₈ alkenyl, phenyl. Further preferably, R ₃ represents a C ₁ -C ₄ linear or branched alkyl group, or a C ₄ -C ₈ cycloalkylalkyl group.

a is preferably an integer of from 1 to 6, more preferably 1, 2, 3 or 4.

As a preferred aspect, in formula (II), R ₄ is selected from C ₁ -C b monovalent straight or branched chain alkyl of _20, C ₂ -C b alkenyl price _20, C ₃ -C ₂₀ a b-valent cycloalkyl group, a C ₄ -C ₂₀ b-valent cycloalkylalkyl group, a C ₄ -C ₂₀ b-valent alkylcycloalkyl group, a C ₆ -C ₂₀ b-valent aryl group, a C ₇ -C ₂₀ b-valent arylalkyl,

Wherein -CH ₂ - may be optionally substituted by -O- or -OCH ₂ CH ₂ - provided that two -O- are not directly bonded; R ₇ and R ₈ each independently represent C ₁ -C ₄ a linear or branched alkylene group, A ₁ and A ₂ each independently represent an empty, C ₁ -C ₄ alkylene group or 1,4-phenylene group, and m ₁ and m ₂ represent an integer of 0-6. .

Further preferably, R _{4 is} selected from a C ₂ -C ₁₂ linear or branched b-valent alkyl group, a C ₂ -C ₈ b-valent alkenyl group, a C ₃ -C ₁₀ b-valent cycloalkyl group, C _{4- C14} b-valent cycloalkylalkyl group, C ₄ -C ₁₄ b-valent alkylcycloalkyl group, C ₆ -C ₁₀ b-valent aryl group, C ₇ -C ₁₂ b-valent arylalkyl group ,

Wherein -CH ₂ - may be optionally substituted by -O-, provided that two -O- are not directly bonded; and R ₇ and R ₈ each independently represent a straight or branched chain of C ₁ -C ₄ The alkyl group, A ₁ and A ₂ each independently represents an empty, C ₁ -C ₄ alkylene group or 1,4-phenylene group, and m ₁ and m ₂ represent an integer of 0-4.

Preferably, B represents -CH ₂ -, -(CH ₂ -CH ₂ -O) _m -CH ₂ -, -[CH ₂ -CH(CH ₃ )-O] _m -CH ₂ -, wherein m represents 0- An integer of 10.

More preferably, m in B represents 0, 1, 2, 3 or 4.

Preferably, R ₅ represents hydrogen, C ₁ -C ₁₀ linear or branched alkyl, C ₂ -C ₈ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₄ -C ₁₀ cycloalkane Alkylalkyl, C ₄ -C ₁₀ alkylcycloalkyl, phenyl.

More preferably, R ₅ represents a C ₁ -C ₄ linear or branched alkyl group, a C ₃ -C ₈ cycloalkyl group, a C ₄ -C ₈ cycloalkylalkyl group, or a phenyl group.

b is preferably an integer from 1 to 6, more preferably 1, 2, 3 or 4.

In a preferred embodiment, in the formula (III), R ₆ represents a C ₁ -C ₂₀ linear or branched c-valent alkyl group, a C ₂ -C ₁₀ c-valent alkenyl group, or a C ₃ -C ₁₀ C-valent cycloalkyl, C ₄ -C ₁₅ c-valent cycloalkylalkyl, C ₄ -C ₁₅ c-valent alkylcycloalkyl, C ₆ -C ₂₀ c-valent aryl, C ₇ -C ₂₀ The c-valent arylalkyl group, wherein -CH ₂ - may be optionally substituted by -O-, -S-.

Further preferably, R ₆ represents a C ₁ -C ₁₀ linear or branched c-valent alkyl group, a C ₂ -C ₈ c-valent alkenyl group, a C ₃ -C ₆ c-valent cycloalkyl group, a C ₄ c divalent -C ₁₀ cycloalkylalkyl, C ₄ -C ₁₀ monovalent c alkylcycloalkyl, c monovalent C ₆ -C ₁₂ aryl group is, C ₇ -C ₁₄ arylalkyl group of monovalent c, Wherein -CH ₂ - may be optionally substituted by -O-.

X is preferably chlorine or bromine.

c is preferably an integer from 1 to 6, more preferably 1, 2, 3 or 4.

Accordingly, the present invention also relates to a process for the preparation of the above novel oxetane compound, comprising: a compound having the structure represented by the formula (I) or (II) in the presence of a catalyst and having the formula (III) The halogenated hydrocarbon of the structure shown undergoes a nucleophilic substitution reaction.

The above preparation method is a conventional reaction for synthesizing a similar compound in the art, and on the basis of knowing the structure and synthesis of the product of the present invention, specific reaction conditions are easily determined by those skilled in the art.

Preferably, the nucleophilic substitution reaction is carried out under reflux; the catalyst used may be selected from the group consisting of alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, etc.; alkali metal salts of alcohols such as sodium methoxide and potassium ethoxide , sodium t-butoxide, etc.; alkali metal hydrogencarbonate, such as sodium hydrogencarbonate, potassium hydrogencarbonate and the like.

Depending on the type of the raw material, an organic solvent may optionally be included in the reaction system to ensure formation of a uniform system. The type of the solvent to be used is not particularly limited as long as it can dissolve the reaction raw material and has no adverse effect on the reaction, and may be, for example, a nitrile solvent such as acetonitrile, propionitrile or benzonitrile; N,N-dimethylformamide, N An amide solvent such as N-dimethylacetamide or N-methylpyrrolidone; an ether solvent such as tetrahydrofuran or dioxane; an aromatic solvent such as benzene, toluene or xylene; and the like. These solvents may be used singly or in combination of two or more. The total amount may be adjusted depending on the homogeneity and stirring property of the reaction system, which is easily determined by those skilled in the art.

After completion of the reaction, the mixture is washed with water, extracted, and distilled under reduced pressure to obtain an oxetane compound of the present invention.

The reaction raw materials used in the above production methods are all known compounds in the prior art, and are commercially available or conveniently prepared by an existing process. The preparation of the compounds of the formulae (I) and (II) is described in detail in Chinese Patent Application No. 201610548580.7 and JP-A No.

The oxetane compound of the present invention may be a monohydroxy compound of the formula (I) (i.e., a = 1) or a compound of the formula (II) (i.e., b = 1) and a monohalogenated compound (i.e., c = 1). Or a polyhalogenated compound (ie c>1), which may also be a polyhydroxy compound of the formula (I) (ie a>1) or a compound of the formula (II) (ie b>1) and a monohalogenated The compound (ie c=1) or the polyhalogenated compound (ie c>1) is obtained by reaction. A wide variety of monofunctional or polyfunctional compounds can be flexibly prepared by adjusting the values of the reactive functional groups, i.e., a, b, and c, in the reaction starting materials.

Accordingly, the present invention also relates to the use of the above novel oxetane compounds in the field of photocuring, particularly in the field of cationic photocuring, and photocurable compositions containing the novel oxetane compounds.

Detailed ways

The present invention will be further specifically described below in conjunction with the examples, but the scope of the invention is not limited to the examples.

Preparation example

Example 1

Preparation of intermediate 1

Into a 250 ml four-necked flask equipped with a stirring device, a thermometer, and a reflux condenser, 58 g (0.5 mol) of a raw material, 1, 4 g (0.1 mol) of sodium hydroxide and 100 g of toluene were successively added, and the mixture was stirred and heated to 80 ° C, and 86 g (0.5 g) was added dropwise. Mol) raw material 2, 1.5h drop addition, continue to stir the reaction, gas phase tracking until the content of raw material 1 no longer changes, stop heating, adjust the pH value to neutral with 5% hydrochloric acid solution, filter, add water and stir well, let stand The aqueous layer was removed twice, and the organic layer was evaporated to remove toluene under reduced pressure to give 136 g of pale yellow liquid.

The structure of Intermediate 1 was confirmed by GC-MS and ¹ H-NMR.

MS (m / e): 289 (M + 1);

¹ H-NMR (CDCl ₃ , 500 MHz): δ 0.96 (6H, m), δ 1.25 (4H, m), δ 2.01 (1H, d), δ 3.29 (4H, s), δ 3.52 (4H, d), δ 3.87 (1H, m), δ 4.65 (8H, s).

Preparation of product 1

144 g (0.5 mol) of intermediate 1, 78 g (1.0 mol) of chloropropane and 20 g (0.5 mol) of sodium hydroxide were sequentially added to a 500 ml four-necked flask equipped with a stirring device, a thermometer, and a reflux condenser, and refluxed for 12 hours. The intermediate 1 was completely disappeared. After completion of the reaction, water was added and stirred well, and the mixture was allowed to stand. The aqueous layer was separated and the mixture was twice. The organic layer was distilled under reduced pressure to remove excess chloropropane, and finally 156 g of a viscous liquid was obtained.

The structure of the product 1 was confirmed by GC-MS and ¹ H-NMR.

MS (m/e): 331 (M + 1);

¹ H-NMR (CDCl ₃ , 500 MHz): δ 0.96 (9H, m), δ 1.25 (4H, m), δ 1.50 (2H, m), δ 3.29-3.51 (11H, m), δ 4 .65 (8H, s).

Example 2

Preparation of product 2

144 g (0.5 mol) of intermediate 1, 44 g (0.25 mol) of p-dichlorobenzyl, 20 g (0.5 mol) of sodium hydroxide and 150 ml of toluene were successively added to a 500 ml four-necked flask equipped with a stirring device, a thermometer, and a reflux condenser. The reflux reaction was carried out, and the gas phase was traced until the intermediate 1 completely disappeared. After the completion of the reaction, water was added and stirred well, and the mixture was allowed to stand, and the aqueous layer was separated. The organic layer was distilled under reduced pressure to remove toluene to obtain 165 g of a viscous liquid.

The structure of the product 2 was confirmed by GC-MS and ¹ H-NMR.

MS (m/e): 679 (M+1);

¹ H-NMR (CDCl ₃ , 500 MHz): δ 0.96 (12H, m), δ 1.25 (8H, m), δ 3.29-3.51 (18H, m), δ 4.63-4.65 (20H, m) , δ 7.12 (4H, d).

Example 3

Preparation of intermediate 2

Into a 500 ml four-necked flask equipped with a stirring device, a thermometer, and a reflux condenser, 58 g (0.5 mol) of a raw material 3, 4 g (0.1 mol) of sodium hydroxide and 100 g of toluene were successively added, and the mixture was stirred and heated to 80 ° C, and 85 g of the solution was added dropwise. (0.25mol) of the toluene solution of the raw material 4, 1.5h dropwise addition, continue to stir the reaction, the gas phase is traced until the content of the raw material 3 does not change, stop heating, adjust the pH to neutral with 5% hydrochloric acid solution, filter, add water fully After stirring, the aqueous layer was separated and allowed to stand twice, and the organic layer was evaporated to remove toluene under reduced pressure to give 136 g of pale yellow liquid.

The structure of the intermediate 2 was confirmed by GC-MS and ¹ H-NMR.

MS (m/e): 573 (M + 1);

¹ H-NMR (CDCl ₃ , 500 MHz): δ 0.96 (6H, m), δ 1.25 (4H, m), δ 1.67 (6H, s), δ 2.01 (2H, s), δ 3.29 - δ 3.52 (8H, m), δ 4.05 - 4.65 (14H, m), δ 6.69 - 7.02 (8H, m).

Preparation of product 3

Into a 500 ml four-necked flask equipped with a stirring device, a thermometer, and a reflux condenser, 143 g (0.25 mol) of Intermediate 2, 76 g (0.5 mol) of 2-bromopentane, 20 g (0.5 mol) of sodium hydroxide and 150 ml of toluene were successively added. The reflux reaction was carried out, and the gas phase was traced until the intermediate 2 disappeared completely. After the completion of the reaction, water was added and stirred well, and the mixture was allowed to stand. The aqueous layer was separated and the mixture was separated twice. The organic layer was distilled under reduced pressure to remove toluene, and finally 162 g of a viscous liquid was obtained.

The structure of the product 3 was confirmed by GC-MS and ¹ H-NMR.

MS (m/e): 714 (M + 1);

¹ H-NMR (CDCl ₃ , 500 MHz): δ 0.96 (12H, m), δ 1.21-1.42 (18H, s), δ 1.67 (6H, s), δ 3.01-3.67 (12H, m) , δ 4.07 (4H, d), δ 4.65 (8H, s), δ 6.69-7.02 (8H, m).

Example 4

Preparation of product 4

Into a 500 ml four-necked flask equipped with a stirring device, a thermometer, and a reflux condenser, 143 g (0.25 mol) of intermediate 2, 50 g (0.25 mol) of 1,3-dibromopropane, 20 g (0.5 mol) of sodium hydroxide and the like were sequentially added. 200ml of toluene, reflux reaction, gas phase tracking until the intermediate 2 completely disappeared, after the reaction is completed, add water and stir well, let stand, separate the water layer, repeat twice, the organic layer is distilled under reduced pressure, toluene is removed, and finally a viscous liquid is obtained. 166g.

The structure of the product 4 was confirmed by IR.

IR (KBr), ν/cm ^-1 : 981(s,

), 1200 (m, COC), 960.7 (m, Ar-H).

Example 5-11

Referring to the method of Examples 1-4, the products having the structures shown in Table 1 were synthesized from the corresponding reagents 5-11.

Table 1

Performance Testing

The application properties of the oxetane compound of the present invention are evaluated by formulating an exemplary photocurable composition, including formulation viscosity, curing speed under different humidity, odor of cured product, adhesion, and the like, and Comparison with the commercially available oxetane compounds OXT-101 and OXE-10.

According to the formulation shown in Table 2, the raw materials were uniformly mixed in a dark room to obtain a photocurable composition. Parts indicated are by mass unless otherwise indicated. The viscosity of each formulation was tested using an NDJ-79A rotational viscometer and the test results are summarized in Table 2.

Table 2

The structural formulas of TTA21, OXT-101, OXE-10 and PAG-202 in Table 2 are as follows:

1. Curing speed under different humidity

The photocurable composition was sampled on a PET substrate, and a 25# bar was coated to obtain a coating having a thickness of about 25 μm, which was exposed to a crawler exposure machine under different humidity conditions (exposure model RW-UV20101) ), a single dose of radiant energy of 20 mj/cm ² was recorded, and the minimum number of times required to cure each formulation was recorded.

During the test, the humidity is controlled by a humidifier and the humidity is monitored by a hygrometer.

The results are shown in Table 3.

table 3

2, odor

The composition was applied to a tinplate at a thickness of 25 μm and subjected to a radiant energy of 200 mj/cm ² to fully cure completely. The residual odor of the cured film was directly evaluated by the nose. The test results are divided into three levels: ○ (no odor), ◎ (with taste), ● (irritating odor).

3, adhesion

The cured film was tested under the conditions of a temperature of 23 ° C and a relative humidity of 50%. According to the standard evaluation method of the paint film according to GB/T9286-1998, the coating film is cut into a hundred grid, the cutting edge should be drawn with the substrate when cutting, and the cutting edge should be sharp, and the cutting edge and the coating film become 45. Degree angle. Use a soft brush to remove the paint scraps, stick the 3M transparent tape on the lined 100 grids, and apply force to make the tape firmly adhere to the film surface and the cross-section. Within 2 min, hold one end of the 3M tape at a 60 degree angle and smoothly peel off the tape within 1 second and evaluate according to the following criteria.

Level 0: The cutting edge is completely smooth and has no shedding;

Level 1: There is a little coating peeling off at the intersection of the incisions, but the cross-cut area is not affected by significantly more than 5%;

Level 2: There is a coating peeling off at the intersection of the incision and/or along the edge of the incision, which is significantly affected by more than 5%, but not significantly greater than 15%;

Level 3: The coating peels off partially or completely along the cutting edge with large fragments, and/or partially or completely peels off at different parts of the lattice. The affected cross-cut area is significantly greater than 15%, but not significantly greater than 35%;

Level 4: The coating peels off along the cutting edge, and/or some of the squares are partially or completely detached, and the affected cross-cut area is significantly greater than 35%, but not significantly greater than 65%;

Level 5: The degree of peeling exceeds level 4.

The performance evaluation results are summarized in Table 4.

Table 4

	Formula 1	Formula 2	Formula 3	Formula 4	Formula 5	Formula 6	Recipe 7
odor	○	○	○	○	○	◎	◎
Adhesion	Level 0	Level 0	Level 0	Level 0	Level 0	Level 1	Level 1

It can be seen from the test results of Table 3 that when the oxetane compound of the present invention is applied to a cationic photocuring system, the humidity change has little effect on the curing speed (i.e., is not sensitive to humidity), from 20% to 40% to 60%, the number of times required for the composition to fully cure is substantially the same. In contrast, with the use of OXT-101 and OXE-10 formulations 6 and 7, as the humidity increased, the curing process was significantly elongated and the curing speed was significantly reduced.

As shown in Table 4, using the oxetane compound of the present invention, the cured product was excellent in odorlessness and adhesion, and had a significant advantage over OXT-101 and OXE-10.

In summary, the novel oxetane compound of the present invention has excellent application performance in a cationic photocuring system, and can effectively compensate for defects such as sensitivity of the cationic curing system to moisture.

Claims (16)

1. An oxetane compound obtained by nucleophilic substitution reaction of a compound having a structure represented by the following formula (I) or (II) with a halogenated hydrocarbon having a structure represented by the formula (III) in the presence of a catalyst to make:

   

   In the general formula (I),

   R ₁ represents a linear or branched a-valent alkyl group of C ₁ -C ₄₀ , an a-valent alkenyl group of C ₂ -C ₂₀ , a a-valent aryl group of C ₆ -C ₄₀ , wherein -CH ₂ - Optionally by -O-, -NH- or

   

   Substituted, provided that the two -O- are not directly linked; and optionally, one or more of the hydrogen atoms of these groups may be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group;

   R ₂ represents a C ₁ -C ₂₀ linear or branched alkylene group, and -CH ₂ - in the main chain may be optionally substituted by -O-, provided that two -O- are not directly linked, and Optionally, one or more hydrogen atoms in the group may each be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group;

   R ₃ represents hydrogen, halogen, nitro, C ₁ -C ₂₀ linear or branched alkyl, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ cycloalkylalkyl, C ₄ -C An alkylcycloalkyl group of ₂₀ , an alkenyl group of C ₂ -C ₁₀ , an aryl group of C ₆ -C ₂₀ , optionally, one or more hydrogen atoms of these groups may each independently be selected from an alkane Substituted by a group of a halogen, a nitro group;

   a represents an integer from 1 to 8;

   In the general formula (II),

   R ₄ means from

   

   a b-valent organic residue obtained by removing b oxirane group structures, a linear or branched b-valent alkyl group selected from C ₁ -C ₄₀ , and a b-valent alkenyl group of C ₂ -C ₄₀ a B-valent cycloalkyl group of C ₃ -C _{40 ,} a b-valent cycloalkylalkyl group of C ₄ -C _{40 ,} a b-valent alkylcycloalkyl group of C ₄ -C _{40 , and} a b-valent aromatic group of C ₆ -C ₄₀ a C ₇ -C ₄₀ b-valent arylalkyl group,

   

   

   Wherein -CH ₂ - may be optionally substituted by -O- or -OCH ₂ CH ₂ - provided that the two -O- are not directly attached;

   R ₇ and R _{8 are the} same or different and each independently represents a C ₁ -C ₁₀ linear or branched alkylene group;

   A ₁ and A _{2 are the} same or different and each independently represents an empty, C ₁ -C ₁₀ alkylene group or a phenylene group;

   m ₁ and m ₂ represent 0 or an integer greater than 0;

   B represents -CH ₂ -, -(CH ₂ -CH ₂ -O) _m -CH ₂ -, -[CH ₂ -CH(CH ₃ )-O) _m -CH ₂ -, wherein m represents 0 or greater than 0 Integer

   R ₅ represents hydrogen, halogen, nitro, C ₁ -C ₂₀ linear or branched alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ a cycloalkylalkyl group, a C ₄ -C ₂₀ alkylcycloalkyl group, a C ₆ -C ₂₀ aryl group, optionally, one or more of the hydrogen atoms of these groups may be independently selected from the group consisting of alkane Substituted by a group of a halogen, a nitro group;

   b represents an integer from 1-8;

   In the general formula (III),

   R ₆ represents a linear or branched c-valent alkyl group of C ₁ -C ₄₀ , a c-valent alkenyl group of C ₂ -C _{20 ,} a c-valent cycloalkyl group of C ₃ -C ₂₀ , or a C ₄ -C ₂₀ a c-valent cycloalkylalkyl group, a C ₄ -C ₂₀ c-valent alkylcycloalkyl group, a C ₆ -C ₄₀ c-valent aryl group, a C ₇ -C ₄₀ c-valent arylalkyl group, a C ₂ -C a c-valent heterocyclic group of ₁₀ , wherein -CH ₂ - may be optionally substituted by -O-, -S-;

   X represents a halogen such as fluorine, chlorine, bromine or iodine;

   c represents an integer from 1-8.
2. The oxetane compound according to claim 1, wherein, in the formula (I), R ₁ represents a C ₁ - C ₂₀ linear or branched a-valent alkyl group, C ₂ - C a divalent alkenyl group, linear or branched _10, C ₆ -C ₃₀ aryl is a monovalent group in which -CH ₂ - may optionally be substituted with -O -, - NH- or

   

   Substituted, provided that the two -O- are not directly linked; and optionally, one or more of the hydrogen atoms of these groups may be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group.
3. The oxetane compound according to claim 1 or 2, wherein R ₁ represents a C ₁ - C ₁₂ linear or branched a-valent alkyl group, a C ₂ - C ₈ linear chain or Branched a-valent alkenyl, C ₆ -C ₃₀ a-valent aryl, wherein -CH ₂ - may be optionally -O-, -NH- or

   

   Substituted, the condition is that two -O- are not directly connected.
4. The oxetane compound according to claim 1, wherein R ₂ represents a C ₁ - C ₁₀ linear or branched alkylene group, and -CH ₂ - in the main chain thereof is optionally Substituted by -O-, provided that two -O- are not directly bonded; preferably, R ₂ represents a C ₁ -C ₆ straight or branched alkylene group, and -CH ₂ - in the main chain The ground is replaced by -O-, provided that the two -O- are not directly connected.
5. The oxetane compound according to claim 1, wherein R ₃ represents hydrogen, a C ₁ - C ₁₀ linear or branched alkyl group, a C ₃ - C ₁₀ cycloalkyl group, C ₄ -C ₁₀ cycloalkylalkyl, alkylcycloalkyl _{C. 4} -C _10, C ₂ -C ₈ alkenyl group, a phenyl group; preferably, R ₃ represents C ₁ -C ₄ linear or Branched alkyl, or C ₄ -C ₈ cycloalkylalkyl.
6. The oxetane compound according to claim 1, wherein a is an integer of from 1 to 6, preferably 1, 2, 3 or 4.
7. The oxetane compound according to claim 1, wherein, in the formula (II), R _{4 is} selected from a C ₁ - C ₂₀ linear or branched b-valent alkyl group, C ₂ - monovalent C b ₂₀ alkenyl, C ₃ -C b cycloalkyl price _20, b divalent C ₄ -C ₂₀ cycloalkylalkyl, b divalent C ₄ -C ₂₀ alkylcycloalkyl, C _6- C ₂₀ b-valent aryl, C ₇ -C ₂₀ b-valent arylalkyl,

   

   

   Wherein -CH ₂ - may be optionally substituted by -O- or -OCH ₂ CH ₂ - provided that two -O- are not directly bonded; R ₇ and R ₈ each independently represent C ₁ -C ₄ a linear or branched alkylene group, A ₁ and A ₂ each independently represent an empty, C ₁ -C ₄ alkylene group or 1,4-phenylene group, and m ₁ and m ₂ represent an integer of 0-6. .
8. The oxetane compound of claim 1 or claim 7, wherein: b R ₄ is selected from divalent linear or branched C ₂ -C ₁₂ chain alkyl, C ₂ -C ₈ divalent B of Alkenyl, C ₃ -C ₁₀ b-valent cycloalkyl, C ₄ -C ₁₄ b-valent cycloalkylalkyl, C ₄ -C ₁₄ b-valent alkylcycloalkyl, C ₆ -C ₁₀ a b-valent aryl group, a C ₇ -C ₁₂ b-valent arylalkyl group,

   

   

   Wherein -CH ₂ - may be optionally substituted by -O-, provided that two -O- are not directly bonded; and R ₇ and R ₈ each independently represent a straight or branched chain of C ₁ -C ₄ The alkyl group, A ₁ and A ₂ each independently represents an empty, C ₁ -C ₄ alkylene group or 1,4-phenylene group, and m ₁ and m ₂ represent an integer of 0-4.
9. The oxetane compound according to claim 1, wherein B represents -CH ₂ -, -(CH ₂ -CH ₂ -O) _m -CH ₂ -, -[CH ₂ -CH(CH) ₃ ) -O] _m -CH ₂ -, wherein m represents an integer of 0-10, preferably m represents 0, 1, 2, 3 or 4.
10. The oxetane compound according to claim 1, wherein R ₅ represents hydrogen, a C ₁ - C ₁₀ linear or branched alkyl group, a C ₂ - C ₈ alkenyl group, or C ₃ -C ₁₀ cycloalkyl, cycloalkylalkyl _{C. 4} -C ₁₀ alkylcycloalkyl _{C. 4} -C _10, phenyl; preferably, R ₅ represents C ₁ -C ₄ linear or Branched alkyl, C ₃ -C ₈ cycloalkyl, C ₄ -C ₈ cycloalkylalkyl, or phenyl.
11. The oxetane compound according to claim 1, wherein b is an integer of from 1 to 6, preferably 1, 2, 3 or 4.
12. The oxetane compound according to claim 1, wherein, in the formula (III), R ₆ represents a C ₁ - C ₂₀ linear or branched c-valent alkyl group, C ₂ - C ₁₀ c-valent alkenyl group, C ₃ -C ₁₀ c-valent cycloalkyl group, C ₄ -C ₁₅ c-valent cycloalkylalkyl group, C ₄ -C ₁₅ c-valent alkylcycloalkyl group, C ₆ divalent aromatic group -C c _20, C c monovalent ₇ -C ₂₀ arylalkyl group, wherein the -CH ₂ - can optionally be -O - substituted S- -,.
13. The oxetane compound according to claim 1 or 12, wherein R ₆ represents a C ₁ - C ₁₀ linear or branched c-valent alkyl group or a C ₂ - C ₈ c-valent chain. Alkenyl, C ₃ -C ₆ c-valent cycloalkyl, C ₄ -C ₁₀ c-valent cycloalkylalkyl, C ₄ -C ₁₀ c-valent alkylcycloalkyl, C ₆ -C ₁₂ c A valent aryl, C ₇ -C ₁₄ c-valent arylalkyl group, wherein -CH ₂ - may be optionally substituted by -O-.
14. The oxetane compound according to claim 1, wherein c is an integer of from 1 to 6, preferably 1, 2, 3 or 4.
15. The process for producing an oxetane compound according to any one of claims 1 to 14, which comprises a compound having a structure represented by the formula (I) or (II) in the presence of a catalyst and having a general formula The halogenated hydrocarbon of the structure shown in (III) undergoes a nucleophilic substitution reaction.
16. Use of the oxetane compound according to any one of claims 1 to 14 in the field of photocuring, in particular in the field of cationic photocuring.