TWI440650B - Polyoxazobenzene cyclohexane oligomers and their application and preparation methods - Google Patents

Description

Polyoxynitride benzocyclohexane oligomer and application and preparation method thereof

The present invention relates to a polyoxonitrobenzocyclohexane oligomer, and more particularly to a polyoxonitrobenzocyclohexane oligomer which is soluble in a medium to low boiling solvent.

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 ( Low Tg), insufficient heat resistance, brittle texture and poor impact resistance.

In order to solve the above problems caused by the preparation of copper foil coated substrates by epoxy resin, a new polymer material has been developed: oxonitrobenzobenzene ring Benzoxazine, which is a kind of Phenol formaldehyde resin, which overcomes some of the shortcomings of traditional phenolic resins and epoxy resins (such as by-products during hardening and the use of strong acids as catalysts, etc.), only When the monomer is heated, the ring is hardened to form a polymer, and no water is released upon hardening. 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.

In 1999, Ishida et al., Macromolecular Chemistry and Physics , 1999, 200 , 1745-1752, published the preparation of oxonitrobenzoxine by the following method: reaction with formaldehyde and aniline at 70 ° C, first formation of triazole The intermediate of the triazine structure, 1,3,5-triarylhexahydro-1,3,5-triazine [1,3,5-triarylhexahydro-1,3,5-triazine], and then synthesized two (3,4-dihydro-2H-3-phenyl-1,3-benzoxazinyl)isopropane [bis(3,4-dihydro-2H-3-phenyl-1,3-benzoxazinyl)isopropane] . Usually, the trinitrogen heterocyclic structure is decomposed by a phenolic compound to form oxoazobenzocyclohexane, but in some cases, the decomposition rate of the triazacyclocycle is insufficient, resulting in a triazine heterocyclic network (triazine). Network) crosslinks, and many gelled insolubles are produced. Therefore, when oxoazobenzocyclohexane is synthesized from an aromatic bisamine, a phenol, and a formaldehyde as a raw material, insoluble matter is generated during the reaction due to the formation of a trinitrogen heterocyclic network structure.

In order to avoid insolubles, Lin et al., in Polymer 2008, 49, 1220, published a three-step process for diamine-based oxo-nitrobenzoxanone. First, an aromatic bisamine is reacted with 2-hydroxybenzaldehyde to form an imine (C=N) bond, and then a C=N double bond is reduced by a reducing agent sodium borohydride (NaBH ₄ ). Finally, a formaldehyde temperature-raising closed loop is added to form a diamine-based benzoxazine based on an aromatic bisamine. Although this method can obtain high purity, high yield of oxoazobenzocyclohexane, expensive reducing agents and complicated steps make the three-step process difficult to be accepted by the industry.

From the above, it is known to develop a process suitable for a copper foil-coated substrate, in particular, an oxo-benzobenzocyclohexane or a polymer thereof which can be dissolved in a solvent commonly used for a copper foil-coated substrate, and at the same time overcome the disadvantages of the prior art method. The development of this novel oxoazobenzocyclohexane or its polymer is still one of the important research goals in the industry.

Taking bisphenol A, diamine and formaldehyde to synthesize oxonitrobenzoxanone as an example, the first step is to form a trinitrogen heterocyclic structure with diamine and formaldehyde, and the reaction rate is R ₁ . The second step is the decomposition of the trinitrogen heterocyclic structure by bisphenol A to form polyoxonitrobenzoxanone, the reaction rate R ₂ .

It can be inferred from the above equation that if R _{1 is} much larger than R ₂ , insoluble matter is formed during the reaction. If R _{1 is} less than R ₂ , the reaction does not form insoluble matter. Therefore, if the rate of R ₁ can be effectively reduced, insoluble matter can be prevented from being generated during the reaction. Since the formation of the triazacyclocycle is caused by the condensation between methylols, if the methylol (-CH ₂ OH) is similarly compounded to methylol (Solvation), the formation of condensation between methylols can be effectively reduced. , to reduce the rate of the trinitrogen heterocycle. According to the above principle, the Republic of China I343395 (Application No. 97129451) utilizes diphenol, diamine and formaldehyde to synthesize polyoxonitrobenzoxan having the following chemical formula in a 1:1:4 manner.

However, in the process of the present invention, it has been found that the polyoxygenated benzobenzocyclohexane synthesized by the above method has poor solubility and cannot be dissolved in a low boiling point solvent such as acetone, methyl ether ketone (MEK), or Commercially available products such as "DOWNAL PM" containing propylene glycol monomethyl ether as a main component produced by DOW Company form a solution having a solid content of 40% or more, thereby limiting its application to a copper foil substrate.

Accordingly, a first object of the present invention is to provide a polyoxygenated benzocyclohexane hexane oligomer suitable for use in the preparation of a copper foil coated substrate.

Thus, the polyoxygenated benzocyclohexane hexane oligomer of the present invention has the structure of formula (I) or (II):

Wherein n ranges from 1 to 30, z ranges from 0 to 30, and R ¹ to R ¹¹ are the same or different and each represents H, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, CF ₃ , phenyl, halogen, or a combination of these; R represents a single bond, -CH ₂ -, , , , , -S-, -O-, , ,

X ¹ and X ² are the same or different and represent , Wherein m ranges from 1 to 100; the benzene ring moiety of the above group is optionally substituted by one or more substituents selected from C ₁ -C ₆ alkyl, CF ₃ , benzene a group, a halogen, a C ₃ -C ₇ cycloalkyl group, or a combination of these.

A second object of the invention is to provide a precursor for forming a cured product.

Thus, the present invention is used to form a cured precursor, comprising a polyoxobenzobenzocyclohexane oligomer as described above and a solvent for dissolving the polyoxonitrobenzoxanone A low boiling point solvent in the oligomer, the medium and low boiling point solvent having a boiling point of 55 to 125 °C.

A third object of the present invention is to provide a cured composition.

Thus, the cured composition of the present invention comprises a precursor as previously described; and an epoxy resin.

A fourth object of the present invention is to provide a cured molded article.

Thus, the cured molded article of the present invention is obtained by subjecting a curing composition as described above to a curing reaction.

A fifth object of the present invention is to provide a process for preparing a polyoxonitrobenzocyclohexane oligomer.

Thus, the present invention provides a method for preparing a polyoxonitrobenzocyclohexane oligomer as described above, comprising: a diamine, a difunctional phenol, a trimeric The aldehyde is prepared by mixing a molar ratio of 1:1.1:4 to 1:2:4, and performing a condensation reaction in the presence of a mixed solvent; wherein the mixed solvent includes a first solvent and a second solvent, the first The solvent is selected from toluene or xylene, and the second solvent is selected from an alcohol solvent or an ether alcohol solvent.

The polyoxo-nitrobenzocyclohexane oligomer of the present invention has a specific structure, and its terminal group is a phenol group, and has good mutual solubility with a medium-low boiling point solvent, and is suitable for producing a copper foil substrate. In addition, the preparation method of the polyoxygenated benzocyclohexane hexane oligomer of the present invention is simple, and only by using an excessive amount of a difunctional phenol and a mixed solvent capable of avoiding insoluble matter formation, the existing method can be overcome. Shortcomings. The cured molded article further obtained by the polyoxygenated benzocyclohexane hexane oligomer of the present invention has high glass transition temperature and good thermal stability, and is extremely industrially valuable.

The polyoxonitrobenzocyclohexane oligomer of the present invention having the structure of formula (I) or (II):

Wherein, the range of n is 1 to 30, the range of z is 0 to 30 (the preferred range of n is 1-9, the preferred range of z is 0 to 10), and R ¹ to R ¹¹ are the same or different and Respectively denotes H, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, CF ₃ , phenyl, halogen, or a combination of these; R represents a single bond, -CH ₂ -, , , , , -S-, -O-, , , X ¹ and X ² are the same or different and represent , Wherein m ranges from 1 to 100; the benzene ring moiety of the above group is optionally substituted by one or more substituents selected from C ₁ -C ₆ alkyl, CF ₃ , benzene a group, a halogen, a C ₃ -C ₇ cycloalkyl group, or a combination of these.

Above substituent Represents 1,2-phenylene, 1,3-phenylene or 1,4-phenylene.

Preferably, the polyoxonitrobenzocyclohexane oligomer has the structure of formula (I). More preferably, the R represents And the X ¹ represents . The structures of three specific examples of the polyoxynitazobenzocyclohexane oligomer of the present invention are as follows:

Preferably, the polyoxonitrobenzocyclohexane oligomer has the structure of formula (II). More preferably, R ⁹ to R ¹¹ represent hydrogen and X ² represents

The present invention is used to form a cured precursor, comprising a polyoxobenzobenzocyclohexane oligomer as described above and a oligomer for dissolving the polyoxobenzobenzocyclohexane. A low boiling point solvent having a boiling point of 55 to 125 ° C. The polyoxonitrobenzocyclohexane oligomer is soluble in the medium and low boiling point solvent.

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

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

The cured composition of the present invention comprises a precursor as described above; and an epoxy resin. In the cured composition, the polyoxygenated benzocyclohexane hexane oligomer contained in the precursor may be regarded as a curing agent, which may occur with the epoxy resin. Curing reaction.

Preferably, the epoxy resin and the polyoxonitrobenzocyclohexane oligomer have an equivalent ratio of 1:0.5 to 1:1.5. When the equivalent ratio is less than 0.5, there is a case where the epoxy group is excessive, and when it is more than 1.5, the workability is poor.

Preferably, the epoxy resin is selected from the group consisting of diglycidyl ether of bisphenol A (DGEBA) and dicyclopentadiene epoxy (DCPD epoxy, commercially available). Products such as the "HP 7200" series produced by DIC, cresol novolac epoxy (CNE), or phenol novolac epoxy (PNE). More preferably, the epoxy resin It is a bisphenol A epoxy resin.

The cured molded article of the present invention is obtained by subjecting a curing composition as described above to a curing reaction. The shape or configuration of the cured molded article may vary depending on the subsequent application.

The preparation method of the polyoxonitrobenzocyclohexane oligomer of the invention comprises: mixing a diamine, a difunctional phenol and a trioxane in a molar ratio of 1:1.1:4 to 1:2:4. Preparing a condensation reaction in the presence of a mixed solvent; wherein the mixed solvent comprises a first solvent and a second solvent, the first solvent is selected from toluene or xylene, and the second solvent is selected from Alcohol solvent or ether alcohol solvent.

In the present invention, by adjusting the amount of the difunctional phenol to be more than the diamine, the terminal groups of the synthesized polyoxynitazobenzocyclohexane oligomer are all phenolic, and are soluble in the medium and low boiling solvents. Suitable for making copper foil coated substrates.

The mixed solvent can effectively prevent insoluble matter from being generated during the reaction. In the reaction, the diamine and the paraformaldehyde form a trinitrogen heterocyclic intermediate, and the trinitrogen heterocyclic structure is decomposed by the difunctional phenol to form a polyoxonitrobenzocyclohexane oligomer. If the decomposition rate of the intermediate is insufficient, it will crosslink with each other to cause a large amount of insoluble matter to be formed; if a solvent mixture of an alcohol solvent or an ether alcohol solvent is used for the dissolution, the trinitrogen heterocycle can be lowered. The rate of formation of the body to avoid insoluble matter.

Preferably, the alcohol solvent is selected from the group consisting of methanol, ethanol, propanol, 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-methoxyethanol, 2-ethoxyethanol, 2,2-dimethoxyethanol, or a combination thereof. 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, and preferably 33 to 67%.

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

Preferably, the difunctional phenol is bisphenol A (4,4'-isopropylidenediphenol, also known as bisphenol A).

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

Preferably, the diamine, the difunctional phenol, and the paraformaldehyde are mixed at a molar ratio of 1:1.5:4 to 1:2:4.

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. Diamine: using diaminophenylmethane (purchased from ACROS, purity 97%); 4,4'-diaminodiphenyl ether (purchased from CHRISKEV); and 2,2-double [ 4-(4-Aminophenol)phenyl]propane (available from CHRISKEV).

2. Bifunctional phenol: bisphenol A, purchased from TCI.

3. Paraformaldehyde: purchased from TCI, with a purity of 90%.

4. Mixed solvents: toluene (purchased from TEDIA, HPLC grade) and ethanol (purchased from TEDIA, HPLC grade).

5. Methanol: purchased from TEDIA, HPLC grade.

6. Epoxy resin: bisphenol A diglycidyl ether (DGEBA), Taiwan Changchun synthetic resin production, model BE188, epoxy equivalent (eew) of 188g / eq.

High-resolution nuclear magnetic resonance (NMR): ¹ H-NMR of the sample was analyzed using dimethyl sulfonium-d ₆ (DMSO-d ₆ ) as a solvent.

Thermogravimetric Loss Analyzer (TGA): Tested under nitrogen and air using a Thermo Cahn Versa Therm with a flow rate of 100 mL/min, a heating rate of 20 °C/min, and a temperature range of 100-800 °C.

Dynamic mechanical analyzer (DMA): using Perkin-Elmer Pyris Diamond, the heating rate is 5 ° C / min, The frequency is 1 Hz, the test method is tension, and the amplitude is 25 μm.

<Examples and Comparative Examples> [Example 1] Synthesis of polyoxonitrobenzocyclohexane oligomers of formula (I-A)

The following reactants were weighed according to the molar ratio of diamine, difunctional phenol and trioxane to 1:1.1:4: 50 g (0.252 mol) of diaminophenylmethane (abbreviated as DDM) and 63.32 g (0.252×1.1). Mol) bisphenol A, 30.29 g (0.252 x 4 mol) of trioxane. The above reactant was added to a three-necked round bottom flask and dissolved in 560 mL of a mixed solvent (a mixture of 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 8 hours. No insoluble matter is produced during the reaction. After the reaction is completed, water 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 to obtain a yellow powder by a vacuum oven. A polyoxynitazobenzocyclohexane oligomer (yield 89%, structure of the following formula (IA), and hereinafter referred to as P(B-ddm) 1.1 .

The above P(B-ddm) 1.1 was analyzed by ¹ H-NMR to obtain a spectrum as shown in Fig. 1. In Fig. 1, an absorption peak of a polyoxygenated benzocyclohexane oligomer having 4.3 and 5.3 ppm was found, and a phenol-based absorption peak was found at 9.2 ppm, and thus it was found that the terminal group was a phenol group.

[Embodiment 2] Synthesis of polyoxonitrobenzocyclohexane oligomers of formula (I-A)

The preparation method and preparation conditions of Example 2 were substantially the same as in Example 1. The difference was that the molar ratio of the diamine, the difunctional phenol, and the paraformaldehyde of Example 2 was 1:1.5:4 (as shown in Table 1). The preparation conditions and properties are detailed in Table 1. Hereinafter referred to as P(B-ddm) 1.5 , the yield was 79%.

The above P(B-ddm) 1.5 was analyzed by ¹ H-NMR to obtain a spectrum as shown in Fig. 2. In Fig. 2, it was found that the absorption peak of the polyoxygenated benzocyclohexane oligomer at 4.3 and 5.3 ppm has a phenol-based absorption peak at 9.2 ppm, and thus it is inferred that the terminal group is a phenol group.

[Comparative Example 1] Synthesis of Polyoxonitrobenzocyclohexane Oligomers with Structure (i)

The preparation method and preparation conditions of Comparative Example 1 were substantially the same as in Example 1. The difference was that the ratio of the diamine, the difunctional phenol, and the triformaldehyde molar of Comparative Example 1 was 1:1.0:4 (as shown in Table 1). The preparation conditions and properties are detailed in Table 1. The structure of the product obtained in Comparative Example 1 was as follows in the formula (i), hereinafter referred to as P(B-ddm) 1.0.

The above P(B-ddm) 1.0 was analyzed by ¹ H-NMR. Figure 3 is a ¹ H-NMR spectrum of samples taken at different reaction times. It can be seen from Fig. 3 that the peak of the trinitrogen heterocycle (4.88 ppm) gradually decreased after 1 hour, and almost disappeared at 8 hours. In Fig. 3, it can be found that there are absorption peaks of polyoxygenated benzocyclohexane oligomers at 4.3 and 5.3 ppm, but no phenol-based absorption peak at 9.0 ppm, so that the terminal phenolic group can be inferred. The ratio is very low.

[Example 3] Synthesis of polyoxonitrobenzocyclohexane oligomers having the structure of formula (I-B)

The molar ratio of diamine, difunctional phenol and trioxane is 1:1.1:4, and the following reactants are weighed: 50 g (0.25 mol) of 4,4'-diaminodiphenyl ether (ODA) 62.7 g (0.25 x 1.1 mol) of bisphenol A and 30 g (0.25 x 4 mol) of trioxane. The above reactant was added to a three-necked round bottom flask and dissolved in 550 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, water 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 to obtain a yellow powder by a vacuum oven. A polyoxynitazobenzocyclohexane oligomer (yield 89%, structure of the following formula (IB), and hereinafter referred to as P(B-oda) 1.1 .

The above P(B-oda) 1.1 was analyzed by ¹ H-NMR to obtain a spectrum as shown in Fig. 4. In Fig. 4, it was found that an absorption peak of a polyoxygenated benzocyclohexane oligomer at 4.3 and 5.3 ppm has a phenol-based absorption peak at 9.2 ppm, and thus it is inferred that the terminal group is a phenol group.

[Example 4] Synthesis of polyoxonitrobenzocyclohexane oligomers having the structure of formula (I-B)

The preparation method and preparation conditions of Example 4 were substantially the same as in Example 3. The difference was that the molar ratio of the diamine, the difunctional phenol, and the paraformaldehyde of Example 4 was 1:1.5:4 (as shown in Table 1). The preparation conditions and properties are detailed in Table 1. Hereinafter referred to as P(B-oda) 1.5 , the yield is 90%.

The above P(B-oda) 1.5 was analyzed by ¹ H-NMR to obtain a spectrum as shown in Fig. 5. In Fig. 5, it can be found that there is an absorption peak of polyoxygenated benzocyclohexane oligomer at 4.3 and 5.3 ppm, and a phenol-based absorption peak at 9.2 ppm, so that it is inferred that the terminal group is Phenolic group.

[Comparative Example 2] Synthesis of polyoxo-nitrobenzocyclohexane oligomers having the structure of formula (ii)

The preparation method and preparation conditions of Comparative Example 2 were substantially the same as in Example 3. The difference was that the ratio of the diamine, the difunctional phenol, and the paraformaldehyde molar of Comparative Example 2 was 1:1.0:4 (as shown in Table 1). The preparation conditions and properties are detailed in Table 1. The structure of the product obtained in Comparative Example 2 was as follows in the formula (ii), hereinafter referred to as P(B-oda) 1.0.

[Example 5] Synthesis of polyoxonitrobenzocyclohexane oligomers of formula (I-C)

The molar ratio of diamine, difunctional phenol and trioxane was 1:1.1:4, and the following reactants were weighed: 50 g (0.12 mol) of 2,2-bis[4-(4-aminophenol)benzene Propylene (abbreviated as BAPP), 30.6 g (0.12 x 1.1 mol) bisphenol A, 14.64 g (0.12 x 4 mol) of trioxane. The above reactant was added to a three-necked round bottom flask and dissolved in 270 mL of a mixed solvent (a mixture of 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 30 hours. No insoluble matter is produced during the reaction. After the reaction is completed, water 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 to obtain a yellow powder by a vacuum oven. A polyoxynitazobenzocyclohexane oligomer (yield 78%, the structure is as follows (IC), and is hereinafter referred to as P(B-bapp) 1.1 .

[Embodiment 6] Synthesis of polyoxonitrobenzocyclohexane oligomers of formula (I-C)

The preparation method and preparation conditions of Example 6 were substantially the same as in Example 5. The difference was that the molar ratio of the diamine, the difunctional phenol, and the paraformaldehyde of Example 6 was 1:1.5:4 (as shown in Table 1). The preparation conditions and properties are detailed in Table 1. Hereinafter referred to as P(B-bapp) 1.5 , the yield was 78%.

[Comparative Example 3] Synthesis of polyoxonitrobenzocyclohexane oligomers having the structure of formula (iii)

The preparation method and preparation conditions of Comparative Example 3 were substantially the same as in Example 5. The difference was that the ratio of the diamine, the difunctional phenol, and the paraformaldehyde molar of Comparative Example 3 was 1:1.0:4 (as shown in Table 1). The preparation conditions and properties are detailed in Table 1. The product obtained in Comparative Example 1 had the structure of the following formula (iii), hereinafter referred to as P(B-bapp) 1.0 , and the yield was 78%.

<Physical test>

The following items were tested for Examples 1 to 6 and Comparative Examples 1 to 3, and the test results were recorded in Table 2.

1. Dissolution test with a solid content of 50% by weight:

5 g of the polyoxygenated benzocyclohexane oligopolymers obtained in Examples 1 to 6 and Comparative Examples 1 to 3, respectively, were dissolved in 5 g of methyl ethyl ketone to prepare a solid content of 50% by weight. Varnish. Finally, it is observed whether the varnish is clear; if it is clarified, it means that the solid content can reach 50% by weight or more; if it is not clear, it means that the solid content cannot reach 50% by weight.

It can be seen from Table 2 that Examples 2, 4 and 6 can meet the requirements for preparing a varnish having a solid content of 50%, and are suitable for the preparation of a copper foil substrate process.

<Application Examples 1 to 4> [Application Example 1] Preparation of polyoxynitride benzocyclohexane / epoxy resin cured product

The P(B-ddm)1.1 prepared in Example 1 was dissolved in methyl ethyl ketone to form a precursor.

The precursor was mixed with an equivalent amount of bisphenol A diglycidyl ether on a hot plate at 160 ° C, and after homogeneous mixing, a cured composition was formed.

The curing composition was heated to 180 ° C, 200 ° C, and 220 ° C for two hours, and then naturally cooled to obtain a polyoxygenated benzocyclohexane / epoxy resin cured product of Application Example 1, and Codename P(B-ddm)-1.1/DGEBA is indicated.

Thermal property assessment

The evaluation items and methods are as follows, and the evaluation results are shown in Table 3.

1. Glass transfer temperature (T _{g for} short):

The glass transition temperature (Tg) of the cured product was measured by dynamic mechanical analysis (DMA). The glass transition temperature needs to be at least 170 ° C to meet the current industry requirements for the quality of high Tg copper foil substrates.

2. 5wt% thermal cracking temperature (Td _{5% for} short):

The 5 wt% thermal cracking temperature of the cured materials under a nitrogen atmosphere was measured by a thermogravimetric analyzer. The 5wt% thermal cracking temperature needs to be at least higher than 300 °C to meet the current requirements for the quality of copper foil substrates.

3. Char yield:

The char yield at 800 ° C under nitrogen was measured.

[Application Examples 2~4] Preparation of polyoxynitride benzocyclohexane / epoxy resin cured product

Application Examples 2 to 4 are P(B-ddm)1.5 , P(B-oda)1.1 and P(B-oda)1.5 prepared in Examples 2, 3 and 4, respectively, which are dissolved in methyl ethyl ketone to form a precursor. .

The precursors were separately mixed with an equivalent amount of bisphenol A diglycidyl ether on a hot plate at 160 ° C, and after homogeneous mixing, a cured composition was formed.

The curing composition was heated to 180 ° C, 200 ° C, and 220 ° C for two hours, and then naturally cooled to obtain a polyoxygenated benzocyclohexane / epoxy resin cured product of Application Examples 2 to 4. They are represented by code numbers P(B-ddm)-1.5/DGEBA, P(B-oda)-1.1/DGEBA, and P(B-oda)-1.5/DGEBA, respectively.

Thermal property assessment

The thermal property evaluation methods of Application Examples 2 to 4 were the same as those of Application Example 1, and the dynamic mechanical analysis charts are shown in Fig. 6, and the evaluation results thereof are shown in Table 3.

As can be seen from Table 3, when Examples 1 to 4 were respectively dissolved in methyl ethyl ketone and mixed with an equivalent amount of DGEBA, the polyoxynitazobenzocyclohexane/epoxy resin cured molded article obtained after curing had a height of up to 227~. The glass transition temperature of 241 ° C, 5 wt% thermal cracking temperature is 373 ~ 394 ° C, coke residual rate is 24 ~ 34%, good thermal stability.

In summary, the terminal group of the polyoxynitazobenzocyclohexane oligomer of the present invention is a phenol group, soluble in a medium and low boiling point solvent, and is suitable for a copper foil substrate process. When used to cure a composition, the resulting cured molded article has high glass transition temperature and good thermal stability and is of great industrial value.

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

1 is a spectrogram showing the ¹ H-NMR spectrum of the polyoxonitrobenzocyclohexane oligomer P(B-ddm) 1.1 of Example 1; FIG. 2 is a spectrum diagram illustrating Example 2 ¹ H-NMR spectrum of polyoxynitazobenzocyclohexane oligomer P(B-ddm) 1.5 ; FIG. 3 is a spectrum diagram illustrating the polyoxynitazobenzocyclohexane of Comparative Example 1. ¹ H-NMR spectrum trace of the oligomer P(B-ddm) 1.0 ; FIG. 4 is a spectrum diagram illustrating the polyoxo-nitrobenzocyclohexane oligomer P(B-oda) 1.1 of Example 3. ¹ H-NMR spectrum; FIG. 5 is a spectrogram showing the ¹ H-NMR spectrum of the polyoxygenated benzocyclohexane hexane P (B-oda) 1.5 of Example 4; A dynamic mechanical analysis diagram illustrating the dynamic mechanical analysis of the polyoxygenated benzocyclohexane/epoxy cured articles of Examples 1 to 4.

Claims (11)

A polyoxonitrobenzocyclohexane oligomer having predominantly the structure of formula (I): Wherein n ranges from 1 to 30, and R ¹ to R ⁸ are the same or different and each represents H, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, CF ₃ , phenyl, halogen, or One of these combinations; R represents a single bond, -CH ₂ -, , , , , -S-, -O-, , X ¹ represents , , Wherein m ranges from 1 to 100; the benzene ring moiety of the above group is optionally substituted by one or more substituents selected from C ₁ -C ₆ alkyl, CF ₃ , benzene a group, a halogen, a C ₃ -C ₇ cycloalkyl group, or a combination of these. The polyoxonitrobenzocyclohexane oligomer according to claim 1, wherein the R represents And the X ¹ represents A precursor for forming a cured product, comprising the polyoxygenated benzocyclohexane oligomer as described in claim 1 and a method for dissolving the polyoxonitrobenzobenzene ring a low boiling point solvent in the hexane oligomer, wherein the medium and low boiling point solvent has a boiling point of 55 to 125 ° C, wherein the medium and low boiling point solvent is selected from the group consisting of acetone, methyl ethyl ketone, propylene glycol monomethyl ether or ethylene glycol monomethyl Ether. According to the precursor of the third aspect of the patent application, the content of the polyoxygenonabenzocyclohexane oligomer is 50% by weight. A curing composition comprising: a precursor as described in claim 3; and Epoxy resin. The cured composition according to claim 5, wherein the epoxy resin and the polyoxygenated benzocyclohexane oligomer have an equivalent ratio of 1:0.5 to 1:1.5. The cured composition according to claim 5, wherein the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, dicyclopentadiene epoxy resin, o-methyl novolac epoxy resin, or Phenolic epoxy resin. A cured molded article obtained by curing a curing composition as described in claim 5 of the patent application. A method for preparing a polyoxo-nitrobenzocyclohexane oligomer according to claim 1, comprising: diamine, difunctional phenol, and paraformaldehyde in a molar ratio of 1:1.1: 4~1:2:4 mixing, obtained by performing a condensation reaction in the presence of a mixed solvent; wherein the mixed solvent comprises a first solvent and a second solvent, 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. The preparation method according to claim 9, wherein the alcohol solvent is selected from the group consisting of methanol, ethanol, propanol, 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, iso Sterol, or a combination of these; the ether alcohol dissolves The agent is selected from the group consisting of propylene glycol methyl ether, 2-methoxyethanol, 2-ethoxyethanol, 2,2-dimethoxyethanol, or a combination thereof. The preparation method according to claim 9, wherein the second solvent accounts for 5 to 95% by weight based on 100% by weight of the mixed solvent.