TWI522362B - Polyoxazobenzene and its application and preparation method - Google Patents

Description

Polyoxynitride benzocyclohexane and application and preparation method thereof

The present invention relates to a polyoxonitrobenzocyclohexane, and more particularly to a polyoxygenated benzocyclohexane which is soluble in a medium to low boiling point solvent and has good storage stability.

In recent years, with the development of various electronic products, printed circuit boards need to have low dielectric loss factor, high modulus of elasticity, high heat resistance, low water absorption, high glass transition temperature and excellent electrical properties. The copper foil coated substrate must also have these properties.

Copper clad laminate (CCL) is the most common type of substrate in general printed circuit boards. It is a kind of reinforcing material soaked into a resin composition, then baked, cut, laminated, and heated. The laminated board is formed by pressing and the like, and the copper foil is coated on one side or both sides of the laminated board to obtain a copper foil coated substrate in a high temperature and high pressure environment. Among them, the resin composition is the main factor affecting the properties of the copper foil coated substrate. Commonly used resins such as epoxy resin, phenolic resin, polyamine formaldehyde, fluorenone and Teflon, and reinforcing materials such as glass fiber cloth, carbon fiber or kewei Kelvar fiber and the like.

Epoxy resin is the most commonly used thermosetting resin for preparing copper foil coated substrates. It has good adhesion strength with reinforcing materials, and does not generate volatiles during hardening. The shrinkage of finished products is small and electrical insulation is good, but the glass transition temperature ( Tg) Low, insufficient heat resistance, brittle texture and poor impact resistance.

In order to solve the above problems caused by preparing a copper foil coated substrate by using an epoxy resin, a new polymer material: Benzoxazine, which belongs to Phenol formaldehyde resin, has been developed. One that overcomes some of the shortcomings of conventional phenolic resins and epoxy resins (such as by-products during hardening, and requires the use of strong acids as catalysts, etc.), which requires only ring-hardening to form a polymer upon heating of the monomer, and No water is released when hardened. In terms of properties, polyoxynitazobenzocyclohexane is superior to phenolic resin in both mechanical and thermal properties, and has high glass transition temperature, high modulus, low hygroscopicity, good electrical properties and flame resistance.

The Patent Application No. 101102202 of the Republic of China provides a polyoxygenated benzocyclohexane which is soluble in medium and low boiling solvents, has a high glass transition temperature and good thermal stability, and is suitable for use in making a copper foil coated substrate. Wherein the polyoxonitrobenzocyclohexane is as follows, the medium and low boiling point solvent such as methyl ethyl ketone:

Wherein, the range of y is from 1 to 30, the range of z is from 0 to 30, and the definitions of R ¹ to R ¹¹ , X ¹ and X ² are referred to in the application.

The terminal group of the above polyoxygenated benzocyclohexane is a phenol group, and although it can be dissolved in a medium-low boiling point solvent, since phenol is a catalyst for inducing ring opening of polyoxonitrobenzocyclohexane. First, if the above polyoxobenzobenzocyclohexane is dissolved in methyl ethyl ketone for a long time, there will be problems of precipitation over time, poor storage stability, and gelation time in the process of manufacturing a copper foil substrate. (gel time) will also decrease with the storage time, causing troubles and inconvenience in manufacturing.

In summary, the development of a solvent which can be dissolved in a copper foil coated substrate and long-term storage stability is good for the preparation of the copper foil coated substrate, and the current industry In terms of the world, there is an urgent need.

Accordingly, it is an object of the present invention to provide a polyoxygenated benzocyclohexane which is soluble in a medium to low boiling point solvent and has good storage stability.

Thus, a first object of the present invention is to provide a polyoxonitrobenzocyclohexane having the structure of formula (I):

Where X represents -CH ₂ -, -O-, , , , or ;q ranges from 6 to 68; Ar represents or ; Y means single bond, -CH ₂ -, , , , , -S-, -O-, , , , , , or n ranges from 1.2 to 10.5; p represents 0 or 1; when p is 1, m is 0, and R ¹ and R ² represent ; when p is 0, then m is 1, and R ¹ and R ² represent .

A second object of the present invention is to provide a polyoxynitrobenzobenzohexane solution for forming a cured product.

Thus, the present invention is used to form a cured product of a polyoxygenated benzocyclohexane solution comprising a polyoxynitazobenzocyclohexane as described above, and a solution for dissolving the polyoxygen. A medium to low boiling point solvent of a nitrogen benzocyclohexane; wherein the medium and low boiling point solvent has a boiling point in the range of 55 to 125 °C.

A third object of the present invention is to provide a process for the preparation of polyoxynitrobenzobenzocyclohexane as described above.

Thus, the preparation method of the polyoxonitrobenzocyclohexane of the present invention comprises: diamine, difunctional phenol, trioxane, and monoamine or monophenol in a molar ratio of 1:1:4+2x: x mixing, obtained by performing a condensation reaction in the presence of a mixed solvent; wherein x ranges from 0.05 to 0.7, the mixed solvent includes a first solvent and a second solvent, and the first solvent is selected from toluene or Xylene, the second solvent is selected from an alcohol solvent or an ether alcohol solvent.

The effect of the present invention is that the polyoxygenated benzocyclohexane having the structure represented by the formula (I) does not contain a phenol group, and can be dissolved in a medium-low boiling solvent suitable for preparing a copper foil substrate for a long time. , good storage stability . In addition, the preparation method of the polyoxygenated benzocyclohexane of the present invention is simple, and only the diamine, the bifunctional phenol, the trioxane, and the monoamine or monophenol are mixed in an appropriate ratio to obtain an end. Polyoxygenated benzocyclohexane which does not contain a phenol group is of great industrial value.

Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: FIG. 1 is a spectrogram illustrating the polyoxynitrobenzobenzocyclohexane (IIA) of Example 2. ¹ H-NMR spectrum of p-0.25; FIG. 2 is a spectrogram illustrating the ¹ H-NMR spectrum of the polyoxonitrobenzocyclohexane (IIB)-p-0.25 of Example 5; Spectrogram showing the ¹ H-NMR spectrum of the polyoxonitrobenzocyclohexane (I'-A)-b-1.5 of Comparative Example 5; and FIG. 4 is a spectrum showing the polyoxygen of Comparative Example 6. ¹ H-NMR spectrum of alkalobenzocyclohexane (I'-B)-b-1.5.

The present invention relates to a polyoxonitrobenzocyclohexane having the structure of formula (I):

Where X represents -CH ₂ -, -O-, , , , or ;q ranges from 6 to 68; Ar represents or ;Y means a single bond, -CH ₂ -, , , , , -S-, -O-, , , , , , or n ranges from 1.2 to 10.5; p represents 0 or 1; when p is 1, m is 0, and R ¹ and R ² represent ; when p is 0, then m is 1, and R ¹ and R ² represent .

Preferably, Y represents ;X means -CH ₂ -, -O-, or .

When the value of n is greater than 10.5, the polyoxonitrobenzocyclohexane is insoluble in the medium and low boiling point solvent. When the n value is from 1.5 to 10.5, the polyoxo-nitrobenzocyclohexane is soluble in a medium-low boiling solvent; preferably, when n ranges from 1.5 to 7.2, the polyoxynitazobenzene The storage of cyclohexane in a medium-low boiling solvent is good and has good thermal properties.

Preferably, Ar represents , and p is 1, m is 0, and R ¹ and R ² represent . At this time, the specific structure of the formula (I) is as shown in the following formula (II):

More preferably, the X represents -CH ₂ -, -O-, and the Y represents .

Preferably, Ar represents And p is 1, m is 0, and R ¹ and R ² represent . At this time, the specific structure of the formula (I) is as shown in the following formula (I-II):

More preferably, the X represents -CH ₂ -, -O-.

Preferably, Ar represents And p is 0, m is 1, and R ¹ and R ² represent . At this time, the specific structure of the formula (I) is as shown in the following formula (I-III):

More preferably, the X represents -CH ₂ -, -O-, and the Y represents .

Preferably, Ar represents And p is 0, m is 1, and R ¹ and R ² represent . At this time, the specific structure of the formula (I) is as shown in the following formula (I-IV):

More preferably, the X represents -CH ₂ -, -O-.

A polyoxynitazobenzocyclohexane solution for forming a cured product, comprising a polyoxonitrobenzocyclohexane as described above, and a solution for dissolving the polyoxonitrogen A medium to low boiling point solvent for benzocyclohexane, wherein the medium and low boiling point solvent has a boiling point in the range of 55 to 125 °C. The polyoxynitazobenzocyclohexane solution can be stably stored for more than one month.

Preferably, the medium and low boiling point solvent is selected from the group consisting of acetone, methyl ethyl ketone, propylene glycol methyl ether, ethylene glycol methyl ether, or the like. One of the combinations. Commercially available products such as "DOWNAL PM" produced by DOW with propylene glycol monomethyl ether as a main component.

Preferably, the polyoxonitrobenzocyclohexane is contained in an amount of 40% by weight or more based on 100% by weight of the total of the polyoxygenated benzocyclohexane solution.

A method for preparing a polyoxygenated benzocyclohexane as described above, comprising: diamine, difunctional phenol, trioxane, and monoamine or monophenol in a molar ratio of 1:1:4+ 2x:x mixed, obtained by performing a condensation reaction in the presence of a mixed solvent; wherein x ranges from 0.05 to 0.7, the mixed solvent includes a first solvent and a second solvent, and the first solvent is selected from Toluene or xylene, the second solvent is selected from an alcohol solvent or an ether alcohol solvent. The polyoxynitazobenzocyclohexane end group obtained by the preparation method of the present invention is not a phenol group (the polyoxynitazobenzocyclohexane terminal group in the present case is as defined above for R ¹ and R ² ) ), soluble in medium and low boiling solvents.

Preferably, x ranges from 0.075 to 0.5. More preferably, the x is 0.25.

Preferably, the diamine is selected from the group consisting of Diaminophenyl methane (DDM), 4,4'-diaminodiphenyl ether (ODA), or 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP).

Preferably, the difunctional phenol is selected from the group consisting of bisphenol A (4,4'-isopropylidenediphenol, also known as bisphenol A) or hydroquinone.

Preferably, the paraformaldehyde may also use formaldehyde or an oligomer thereof.

Preferably, the first solvent is toluene.

Preferably, the alcohol solvent is selected from the group consisting of methanol, ethanol, and C. Alcohol, isopropanol, n-butanol, isobutanol, ethylene glycol, n-pentanol, isoamyl alcohol, n-hexanol, 2-hexanol, cyclohexanol, cyclopentanol, n-heptanol, 2-heptanol , n-octanol, isooctanol, n-nonanol, isodecyl alcohol, n-nonanol, isodecyl alcohol, or a combination thereof; the ether alcohol solvent is selected from the group consisting of propylene glycol methyl ether, 2-methoxy Ethanol, 2-ethoxyethanol, 2,2-dimethoxyethanol, or a combination of these. More preferably, the alcohol solvent is ethanol.

Preferably, the second solvent accounts for 5 to 95% by weight based on 100% by weight of the mixed solvent. More preferably, the weight ratio of the first solvent to the second solvent is 2:1.

The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.

<Chemicals and Instruments>

1. Diaminophenylmethane: purchased from ACROS, with a purity of 97%.

2. 4,4'-Diaminodiphenol ether: purchased from CHRISKEV

3. 2,2-Bis[4-(4-Aminophenol)phenyl]propane: purchased from CHRISKEV.

4. Bisphenol A: purchased from TCI.

5. Hydroquinone: purchased from TCI.

6. Mixed solvent: toluene (purchased from TEDIA, HPLC grade) and ethanol (purchased from TEDIA, HPLC grade).

7. Xylene: purchased from TEDIA, HPLC grade.

8. 1,4-dioxane: purchased from TEDIA, HPLC grade.

9. Methanol: purchased from TEDIA, HPLC grade.

10. The high-resolution nuclear magnetic resonance apparatus (NMR): in dimethyl sulfoxide -d ₆ (DMSO-d ₆₎ as solvent ¹ H-NMR analysis of the sample.

[Example 1]

Synthesis of polyoxynitazobenzocyclohexane having the structure of formula (I)

The following reactants were weighed according to the molar ratio of diamine, difunctional phenol, trioxane and monoamine: 1:1:4.1:0.05: 3.0 g (0.015 mol) of 4,4'-diaminodiphenol ether (ODA for short), 3.4202 g (0.015 mol) bisphenol A, 1.8446 g (0.015 x 4.1 mol) trioxane, 0.0705 g (0.015 x 0.05 mol) phenol. The above reactant was added to a three-necked round bottom flask and dissolved in 30 mL of a mixed solvent (obtained by mixing toluene and ethanol, wherein the weight ratio of toluene:ethanol was 2:1).

The three-necked round bottom bottle was purged with nitrogen and heated to 80 ° C with continuous stirring for a reaction time of 16 hours. No insoluble matter is produced during the reaction. After the reaction is completed, methanol is added to the three-necked round bottom bottle, and a strip of product is precipitated; then, stirring is continued, at which time the strip product is converted into a yellow powder, which is then filtered by suction to remove the yellow powder. Finally, the yellow powder was purified by a Soxhlet extractor and a solid crude product was obtained by suction filtration, and then the solid crude product was vacuum dried at 105 ° C using a vacuum oven to obtain 5.71 g of a yellow color. The powdery polyoxonitrobenzocyclohexane was obtained in a yield of 80%, and the structure was represented by the following formula (IIA)-p, and the code was (IIA)-p-0.05.

[Examples 2 and 3] Synthesis of polyoxynitazobenzocyclohexane having the structure of formula (I)

The preparation methods and preparation conditions of Examples 2 and 3 were substantially the same as in Example 1. The difference is that the molar ratio of the diamine, the difunctional phenol, the trioxane and the monophenol of Example 2 is 1:1:4.5:0.25, the diamine of the example 3, the difunctional phenol, the trimerization The molar ratio of formaldehyde to monophenol is 1:1:5.4:0.7.

The product structures of Examples 2 and 3 are all shown in the formula (IIA)-p, which is the same as in Example 1, wherein the product of Example 2 is coded (IIA)-p-0.25; the code of the product of Example 3 is (IIA)-p-0.7. The preparation conditions, yield and yield are detailed in Table 1.

[Examples 4 to 6] Synthesis of polyoxynitazobenzocyclohexane having the structure of formula (I)

The preparation methods and preparation conditions of Examples 4 to 6 were substantially the same as those of Example 1, except that the molar ratios of diamine, difunctional phenol, trioxane and monophenol were 1:1:4.1:0.05, respectively. 1:1:4.5:0.25, and 1:1:5.4:0.7, and the diamine is diaminophenylmethane (DDM). The preparation conditions, yield and yield are detailed in Table 1.

The polyoxynitazobenzocyclohexane obtained in Examples 4 to 6 was in the form of a yellow powder, and the structure is represented by the following formula (I-I-B)-p, and the code is (I-I-B)-p-0.05, respectively. (I-I-B)-p-0.25, and (I-I-B)-p-0.7.

[Examples 7 to 9] Synthesis of polyoxynitazobenzocyclohexane having the structure of formula (II)

Example 7 is based on a molar ratio of diamine, difunctional phenol, trioxane, and monophenol of 1:1:4.1:0.05: 3.0 g (0.015 mol) of 4,4'-diamine Diphenol ether, 1.6499 g (0.015 mol) hydroquinone, 1.8446 g (0.015 x 4.1 mol) trioxane, 0.0705 g (0.015 x 0.05 mol) phenol. The above reactant was added to a three-necked round bottom flask and dissolved in 30 mL of a mixed solvent (mixed toluene and ethanol in which the weight ratio of toluene:ethanol was 2:1).

The three-necked round bottom bottle was purged with nitrogen and heated to 80 ° C with continuous stirring for a reaction time of 16 hours. No insoluble matter is produced during the reaction. After the reaction is completed, methanol is added to the three-necked round bottom bottle, and a strip of product is precipitated; then, stirring is continued, at which time the strip product is converted into a yellow powder, which is then filtered by suction to remove the yellow powder. Finally, the yellow powder was purified by a Soxhlet extractor and a solid crude product was obtained by suction filtration, and the solid crude product was vacuum dried at 105 ° C to obtain a yellow powder. The polyoxonitrobenzocyclohexane was 4.08 g in a yield of 76%, and the structure is represented by the following formula (I-II-A)-p, and the code is (I-II-A)-p-0.05.

The preparation methods and preparation conditions of Examples 8 and 9 are substantially the same as those of Example 7, and the product structure is also shown by the formula (I-II-A)-p; the difference is the molar ratio of the reactants, which is obtained. The polyoxynitride benzocyclohexane codes are (I-II-A)-p-0.25 and (I-II-A)-p-0.7, respectively. The preparation conditions, yield and yield are detailed in Table 1.

[Examples 10 to 12] Synthesis of polyoxynitazobenzocyclohexane having the structure of formula (II)

The preparation methods of Examples 10 to 12 were substantially the same as those of Example 7, except that the molar ratio of the reactants was used, and the diamine was a diaminophenylmethane. The preparation conditions, yield and yield are detailed in Table 1.

The polyoxynitazobenzocyclohexane obtained in Examples 10 to 12 was in the form of a yellow powder having the structure shown by the following formula (I-II-B)-p, and the code is (I-II-B)- P-0.05, (I-II-B)-p-0.25, and (I-II-B)-p-0.7.

[Examples 13 to 15] Synthesis of polyoxynitazobenzocyclohexane having the structure of formula (III)

Example 13 is that the ratio of the Emol is 1:1:4.1:0.05. Reagents: 3.0 g (0.015 mol) of 4,4'-diaminodiphenol ether, 3.4202 g (0.015 mol) of bisphenol A, 1.8446 g (0.015 x 4.1 mol) of trioxane, 0.0698 g (0.015 x 0.05 mol) )aniline. The above reactant was placed in a three-necked round bottom flask and dissolved in 30 mL of a mixed solvent (mixed toluene and ethanol, wherein the weight ratio of toluene:ethanol was 2:1).

The three-necked round bottom bottle was purged with nitrogen and heated to 80 ° C with continuous stirring for a reaction time of 16 hours. No insoluble matter is produced during the reaction. After the reaction is completed, methanol is added to the three-necked round bottom flask, and a strip of product is precipitated; then, stirring is continued, at which time the strip product is converted into a yellow powder, and then the yellow powder is taken out by suction filtration. Finally, the yellow powder was purified by a Soxhlet extractor and a solid crude product was obtained by suction filtration, and the solid crude product was vacuum dried at 105 ° C using a vacuum oven to obtain 5.71 g of a yellow color. The powdery polyoxonitrobenzocyclohexane has a yield of 80% and has the structure of the formula (I-III-A)-q, code (I-III-A)-q-0.05.

The preparation methods and preparation conditions of Examples 14 and 15 are substantially the same as those of Example 13, and the product structure is also shown by the formula (I-III-A)-q; the difference is the molar ratio of the reactants, and the codes are respectively (I-III-A)-q-0.25, and (I-III-A)-q-0.7. The preparation conditions, yield and yield are detailed in Table 1.

[Examples 16 to 18] Synthesis of polyoxynitazobenzocyclohexane having the structure of formula (III)

The preparation methods and preparation conditions of Examples 16 to 18 were substantially the same as in Example 13. The difference is in the molar ratio of the reactants, and the diamine is diaminophenylmethane. The preparation conditions, yield and yield are detailed in Table 1.

The polyoxynitazobenzocyclohexane obtained in Examples 16 to 18 was in the form of a yellow powder having the structure shown by the following formula (I-III-B)-q, and the code is (I-III-B)- Q-0.05, (I-III-B)-q-0.25, and (I-III-B)-q-0.7.

[Examples 19 to 21] Synthesis of polyoxynitazobenzocyclohexane having the structure of formula (IV)

Example 19 was obtained by weighing the following reactants at an IX:4.1:0.05 ratio: 3.0 g (0.015 mol) of 4,4'-diaminodiphenol ether, 1.6497 g (0.015 mol) of hydroquinone. 1.8446 g (0.015 x 4.1 mol) of trioxane, 0.0698 g (0.015 x 0.05 mol) of aniline. The above reactant was placed in a three-necked round bottom flask and dissolved in 30 mL of a mixed solvent (mixed toluene and ethanol, wherein the weight ratio of toluene:ethanol was 2:1).

The three-necked round bottom bottle was purged with nitrogen and heated to 80 ° C with continuous stirring for a reaction time of 16 hours. No insoluble matter is produced during the reaction. After the reaction is completed, methanol is added to the three-necked round bottom bottle, and a strip product is precipitated; Stirring is then continued, at which point the strip product will be converted to a yellow powder which is then filtered off with suction to remove the yellow powder. Finally, the yellow powder was purified by a Soxhlet extractor and a solid crude product was obtained by suction filtration, and the solid crude product was vacuum dried at 105 ° C using a vacuum oven to obtain 5.71 g of a yellow color. The powdery polyoxonitrobenzocyclohexane has a yield of 80% and has the structure of the formula (I-IV-A)-q, code (I-IV-A)-q-0.05.

The preparation methods and preparation conditions of Examples 20 and 21 are substantially the same as those of Example 19, and the product structure is also shown by the formula (I-IV-A)-q; the difference is the molar ratio of the reactants, which is obtained. The codes of polyoxynitrobenzobenzohexane are (I-IV-A)-q-0.25, and (I-IV-A)-q-0.7, respectively. The preparation conditions, yield and yield are detailed in Table 1.

[Examples 22 to 24] Synthesis of polyoxynitazobenzocyclohexane having the structure of formula (IV)

The preparation methods and preparation conditions of Examples 22 to 24 were substantially the same as in Example 19 except that the molar ratio of the reactants was used, and the diamine was diaminophenylmethane. The preparation conditions and properties are detailed in Table 1.

The polyoxynitazobenzocyclohexane obtained in Examples 22 to 24 was in the form of a yellow powder, and the structure is represented by the following formula (I-IV-B)-q, and the code numbers are respectively (I-IV-B)-q-0.05, (I-IV-B)-q-0.25, and (I-IV-B)-q-0.7.

[Comparative Examples 1 to 10]

The preparation methods and preparation conditions of Comparative Examples 1 to 10 were substantially the same as those in Example 1, except that the monoamine or the monophenol compound was not used. The reactant types and molar ratios of Comparative Examples 1 to 10 are described in detail in Table 1.

The polyoxynitazobenzocyclohexane prepared in Comparative Examples 1 to 10 was yellow powder, and the product structure and code were respectively shown in the following formula: The code of Comparative Example 1 was (I'-A), and the structure was as follows: :

The code of Comparative Example 2 is (I'-B) and the structure is as follows:

The code of Comparative Example 3 is (I'-A)-b-1.1, and the code of Comparative Example 5 is (I'-A)-b-1.5, and the structure is as follows:

The code of Comparative Example 4 is (I'-B)-b-1.1, and the code of Comparative Example 6 is (I'-B)-b-1.5. The structure is as follows:

The code of Comparative Example 7 is (I'-A)-a-1.1, and the code of Comparative Example 9 is (I'-A)-a-1.5, and the structure is as follows:

The code of Comparative Example 8 is (I'-B)-a-1.1, and the code of Comparative Example 10 is (I'-B)-a-1.5, and the structure is as follows:

[Comparative Examples 11 to 18]

The preparation methods and preparation conditions of Comparative Examples 11 to 18 were substantially the same as those of Example 1, except that the molar ratio of the reactants, that is, the diamine, the difunctional phenol, the trioxane, and the monoamine or monophenol moir. The ratio is 1:1:4+2x:x, where x is less than 0.05.

The reactant species, molar ratio and reaction conditions of Comparative Examples 11 to 18 are detailed. It is described in detail in Table 1. The product structure and code are the same as those in the previous examples, and are described as follows: The code of Comparative Example 11 is (IIA)-p-0.01, and the product structure is the same as that of Examples 1 to 3, as in the above formula ( IIA)-p is shown; the code of Comparative Example 12 is (IIB)-p-0.01, the product structure is the same as that of Examples 4 to 6, as shown by the above formula (IIB)-p; the code of Comparative Example 13 is (I) -II-A)-p-0.01, the product structure is the same as in Examples 7 to 9, as shown by the above formula (I-II-A)-p; the code of Comparative Example 14 is (I-II-B)-p -0.01, the product structure is the same as that of Examples 10 to 12, as shown by the above formula (I-II-B)-p; the code of Comparative Example 15 is (I-III-A)-q-0.01, product structure and implementation Examples 13 to 15 are the same as shown in the above formula (I-III-A)-q; the code of Comparative Example 16 is (I-III-B)-q-0.01, and the product structure is the same as that of Examples 16 to 18, such as The above formula (I-III-B)-q is shown; the code of Comparative Example 17 is (I-IV-A)-q-0.01, and the product structure is the same as that of Examples 19 to 21, as in the above formula (I-IV- A) is represented by -q; the code of Comparative Example 18 is (I-IV-B)-q-0.01, and the product structure is the same as that of Examples 22 to 24, as shown by the above formula (I-IV-B)-q.

[Comparative Examples 19 to 42]

The reactant types, the reactant molar ratios, and the preparation methods of Comparative Examples 19 to 24 were respectively the same as those of Examples 1 to 24, respectively, that is, Comparative Example 19 is a corresponding Example 1, and Comparative Example 20 is a corresponding Example 2. And so on], the only difference is the type of solvent: Comparative Examples 19 to 24 are made using toluene. It is a solvent.

In Comparative Examples 19 to 24, insoluble matter was generated during the course of the reaction, so that no subsequent precipitation or the like was carried out.

[Comparative Examples 43 to 66]

The reactant species, the molar ratio of the reactants, and the preparation method of Comparative Examples 43 to 66 were respectively the same as those of Examples 1 to 24, respectively, that is, Comparative Example 43 is the corresponding Example 1, and Comparative Example 44 is the corresponding Example 2. And so on, the only difference is the kind of solvent: Comparative Examples 43 to 66 use xylene as a solvent.

In Comparative Examples 43 to 66, insoluble matter was generated during the course of the reaction, so that no subsequent precipitation or the like was carried out.

[Comparative Examples 67 to 90]

The reactant species, the reactant molar ratio, and the preparation method of Comparative Examples 43 to 66 were respectively the same as those of Examples 1 to 24, respectively, that is, Comparative Example 67 is the corresponding Example 1, and Comparative Example 68 is the corresponding Example 2, By analogy, the only difference is the type of solvent: Comparative Examples 43 to 66 use 1,4-dioxane as a solvent.

In Comparative Examples 67 to 90, insoluble matter was generated during the course of the reaction, so that no subsequent precipitation or the like was carried out.

<Structure identification>

The products obtained in Examples 2 and 5 and Comparative Examples 5 and 6 were identified by ¹ H-NMR, and the results are shown in Figures 1, 2, 3 and 4, respectively, and analyzed as follows: Figure 1 and Figure 3 were compared. It can be found that there are absorption peaks of polyoxygenated benzocyclohexane at both 4.3 and 5.3 ppm. In Fig. 3, there is a significant phenol-based absorption peak at 9.2 ppm, and it is understood that the product of Comparative Example 5 has a phenol group. In contrast, in Fig. 1, the phenolic absorption peak at 9.2 ppm is not significant, so it can be inferred that the terminal group is not a phenol group.

2 and 4, the same results as in Figs. 1 and 3 were observed: the phenol-based absorption peak at 9.2 ppm in Fig. 2 was relatively inconspicuous, and it was inferred that the terminal group was not a phenol group.

<Physical test>

Examples 1 to 24 and Comparative Examples 1 to 18 were tested in accordance with the following items, and the test results were recorded in Table 2.

Solubility test for medium and low boiling point solvents: 5 g of the polyoxygenated benzocyclohexanes prepared in Examples 1 to 24 and Comparative Examples 1 to 18 were respectively weighed and dissolved in 5 g of methyl ethyl ketone to observe whether or not Soluble; if soluble, the time for precipitation is further recorded.

Dissolution test with a solid content of 50% by weight: 5 g of the polyoxygenated benzocyclohexanes prepared in Examples 1 to 24 and Comparative Examples 1 to 18, respectively, were dissolved in 5 g of methyl ethyl ketone to prepare A varnish having a solid content of 50% by weight was prepared, and finally, it was observed whether the varnish was clear.

If the varnish is clear and does not precipitate after standing, it means that the solid content can reach 50% by weight or more. It can be applied to the copper foil substrate process, and is marked as "achieved" in Table 2; if the varnish is not clear, This indicates that the solid content cannot be 50% by weight and cannot be applied to the copper foil substrate process, and is described as "unachieved" in Table 2.

The quality is not soluble and therefore not recorded.

First, a mixed solvent of toluene:ethanol in a weight ratio of 2:1 was used with respect to Examples 1 to 24 and Comparative Examples 1 to 18, and Comparative Examples 19 to 90 used a single type of solvent to synthesize polyoxygen. Nitrobenzene benzocyclohexane, and whether or not toluene, xylene or 1,4-dioxane, is used, insoluble matter is formed during the reaction, and thus the product cannot be obtained.

As can be seen from Table 2, Comparative Examples 1 and 2 were only slightly soluble in methyl ethyl ketone and could not be formulated into a varnish having a solid content of 50% by weight because the reactants of Comparative Examples 1 and 2 had the same molar ratio of bisamine and bisphenol. The segments were longer and the molecular weight was higher; Comparative Examples 3 to 10 were soluble in methyl ethyl ketone, but precipitated after a few days, and the storage stability was poor. Comparative Examples 11 to 18 were structurally and in Examples 1 to 24 Similarly, the terminal does not contain a phenol group, but the monoamine or monophenol has a molar ratio of only 0.01, resulting in a longer segment of the product and a higher molecular weight, so that it is only slightly soluble in methyl ethyl ketone and cannot be formulated into a solid content of 50% by weight. Varnish.

The polyoxonitrobenzocyclohexanes of Examples 1 to 24 are all soluble in methyl ethyl ketone, the precipitation time is more than one month, the storage stability is good, and the requirement for preparing a varnish having a solid content of 50% can be achieved, Suitable for copper foil substrate process.

In summary, the polyoxygenated benzocyclohexane of the present invention is prepared by a condensation reaction using a suitable molar ratio of a diamine, a difunctional phenol, a trioxane, and a monoamine or a monophenol. The group is not a phenolic group. It is soluble in medium and low boiling point solvents for more than one month. It has good storage stability and is of great industrial value, so it can achieve the purpose of the present invention.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.

Claims (5)

A method for preparing polyoxo-nitrobenzocyclohexane, comprising: mixing a diamine, a difunctional phenol, a trioxane, and a monoamine or a monophenol in a molar ratio of 1:1:4+2x:x, Prepared by performing a condensation reaction in the presence of a mixed solvent; wherein x ranges from 0.05 to 0.7, the mixed solvent includes a first solvent and a second solvent, and the first solvent is selected from toluene or xylene. The second solvent is selected from the group consisting of an alcohol solvent or an ether alcohol solvent; and the structure of the polyoxonitrobenzocyclohexane is selected from the following formula (II), the following formula (I-II), and Formula (I-III) or the following formula (I-IV): In the formulae (II), (I-II), (I-III) and (I-IV), X represents -CH ₂ - or -O-, and Y represents a single bond, -CH ₂ -, ,or And n ranges from 1.2 to 10.5. The production method according to claim 1, wherein x ranges from 0.075 to 0.5. The preparation method according to claim 1, wherein the alcohol solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, n-pentanol, and isoamyl alcohol. , n-hexanol, 2-hexanol, cyclohexanol, cyclopentanol, n-heptanol, 2-heptanol, n-octanol, isooctanol, n-nonanol, isodecyl alcohol, n-nonanol, isodecyl alcohol, Or a combination of the above; the ether alcohol solvent is selected from the group consisting of propylene glycol methyl ether, 2-methoxyethanol, 2-ethoxyethanol, 2,2-dimethoxyethanol, or a combination thereof . The production method according to claim 1, wherein the second solvent accounts for 5 to 95% by weight based on 100% by weight of the mixed solvent. The production method according to claim 1, wherein n ranges from 1.5 to 7.2.