TWI709585B - Self-curable epoxy resins composition, preparation method thereof and epoxy curable product prepared thereby - Google Patents

Abstract

The present disclosure provides a self-curable epoxy resins composition. The self-curable epoxy resins composition includes a nitrogen containing catalyst and an epoxy. In particular, the epoxy has a structure represented by formula (I) or formula (II). Accordingly, a secondary alcohol can be avoided for curing the epoxy. Thus, a resulting thermosets prepared by the above mentioned self-curable epoxy resins composition exhibits low-dissipation constant, low-dissipation factor and thermal stability.

Description

Self-curable epoxy resin composition, its preparation method and Prepared epoxy cured product

The present invention relates to a self-curable epoxy resin composition, its preparation method and the prepared epoxy cured product, and in particular to a self-curable epoxy resin composition containing a nitrogen-containing catalyst and epoxy resin , Its preparation method and the epoxy cured product prepared.

Traditionally, epoxy resin has been used in coatings, encapsulation, composite materials, copper clad laminates and other fields, because it has excellent performance after curing, usually epoxy resin needs to react with curing agent or hardener to obtain high performance The thermosetting material. However, most of the starting materials of commercial epoxy resins are petroleum-based materials. Due to limited petroleum storage and the increasingly serious environmental pollution problem, relevant industries have begun to look for renewable materials to replace petrochemical raw materials. Renewable materials are renewable, The advantages of large production volume and wide distribution are beneficial to reduce the consumption of non-renewable resources by polymer materials.

In addition, when the epoxy resin is cured with a hardener containing active hydrogen, the epoxy group will form a secondary alcohol after ring opening, and the high polarity of the secondary alcohol will increase. Adding the dissipation factor of the material, the dissipation factor is proportional to the signal transmission loss. Therefore, compared with other low-dielectric polymer materials, epoxy resin thermoset materials generally do not have better dielectric properties.

In view of this, how to prepare an epoxy resin without adding a curing agent or hardener to improve its dielectric properties has become the goal of the relevant industry.

One purpose of the present invention is to provide a self-curable epoxy resin composition, its preparation method and the epoxy cured product prepared therefrom. Renewable materials are used as starting materials to synthesize epoxy resin, and then combined with a catalyst to form Self-curing epoxy resin composition makes it have low dielectric loss.

其中R¹為式(i)、式(ii)、式(iii)或式(iv)所示之一結構：

R²為氫、碳數1至6的烷基、碳數1至6的氧烷基或苯基，n為1至4的整數，m為2至12的整數；當n為2時，R¹為式(i)、式(ii)或式(iii)所示之結構，當n為3時，R¹為式(iv)所示之結構。 One embodiment of the present invention provides a self-curing epoxy resin composition, comprising a nitrogen-containing catalyst and an epoxy resin, wherein the nitrogen-containing catalyst is selected from dimethyldiaminopyridine, imidazole and dimethyl A group consisting of imidazole, epoxy resin has a structure as shown in formula (I) or formula (II):

Where R ¹ is one of the structures shown in formula (i), formula (ii), formula (iii) or formula (iv):

R ² is hydrogen, an alkyl group having 1 to 6 carbons, an oxyalkyl group having 1 to 6 carbons, or a phenyl group, n is an integer from 1 to 4, and m is an integer from 2 to 12; when n is 2, R ¹ is the structure represented by formula (i), formula (ii) or formula (iii), when n is 3, R ¹ is the structure represented by formula (iv).

According to the self-curable epoxy resin composition described in the preceding paragraph, the content of the nitrogen-containing catalyst can be 0.1 wt% to 2.0 wt%.

According to the self-curable epoxy resin composition described in the preceding paragraph, the epoxy resin may have formula (I-1), formula (I-2), formula (I-3), formula (I-4), One of the structures represented by formula (I-5), formula (II-1), formula (II-2), formula (II-3), formula (II-4) or formula (II-5):

其中，m為2至12的整數。

Wherein, m is an integer of 2-12.

Another embodiment of the present invention provides a method for preparing a self-curable epoxy resin composition, which includes providing a renewable raw material, performing an esterification reaction step, performing an epoxidation reaction step, and performing a catalytic step. The renewable raw material may be a phenolic compound, and the esterification reaction step is to react the phenolic compound with a chlorine compound to form an active ester-containing acrylic compound. The epoxidation reaction step is to react the acrylic compound containing the active ester with a metachloroperoxybenzoic acid to epoxidize the double bond at the end of the acrylic compound containing the active ester to form an epoxy resin. Finally, in the catalyzing step, the epoxy resin is added to a nitrogen-containing catalyst to form the self-curable epoxy resin composition, wherein the nitrogen-containing catalyst is selected from the group consisting of dimethyldiazapyridine and imidazole. A group consisting of dimethylimidazole.

其中R²為氫、碳數1至6的烷基、碳數1至6的氧烷基或苯基。 According to the preparation method of the self-curing epoxy resin composition described in the preceding paragraph, the phenolic compound may have a structure as shown in formula (a1) or formula (a2):

Wherein R ² is hydrogen, an alkyl group having 1 to 6 carbons, an oxyalkyl group having 1 to 6 carbons, or a phenyl group.

其中R¹為式(i)、式(ii)、式(iii)或式(iv)所示之一結構：

m為2至12的整數。 According to the preparation method of the self-curable epoxy resin composition described in the preceding paragraph, the chlorinated compound may have a structure as shown in formula (b1) or formula (b2):

Where R ¹ is one of the structures shown in formula (i), formula (ii), formula (iii) or formula (iv):

m is an integer from 2 to 12.

其中R¹為式(i)、式(ii)、式(iii)或式(iv)所示之一結構：

R²為氫、碳數1至6的烷基、碳數1至6的氧烷基或苯基，n為1至4的整數，m為2至12的整數；當n為2時，R¹為式(i)、式(ii)或式(iii)所示之結構，當n為3時，R¹為式(iv)所示之結構。 According to the preparation method of the self-curable epoxy resin composition described in the preceding paragraph, the acrylic compound containing the active ester may have a structure as shown in formula (1) or formula (2):

Where R ¹ is one of the structures shown in formula (i), formula (ii), formula (iii) or formula (iv):

R ² is hydrogen, an alkyl group having 1 to 6 carbons, an oxyalkyl group having 1 to 6 carbons, or a phenyl group, n is an integer from 1 to 4, and m is an integer from 2 to 12; when n is 2, R ¹ is the structure represented by formula (i), formula (ii) or formula (iii), when n is 3, R ¹ is the structure represented by formula (iv).

According to the preparation method of the self-curable epoxy resin composition described in the preceding paragraph, the content of the nitrogen-containing catalyst can be 0.1 wt% to 2.0 wt%.

According to the preparation method of the self-curable epoxy resin composition described in the preceding paragraph, the epoxy resin can have the formula (I-1), formula (I-2), formula (I-3), formula (I- 4) One of the structures shown in formula (I-5), formula (II-1), formula (II-2), formula (II-3), formula (II-4) or formula (II-5):

其中，m為2至12的整數。

Wherein, m is an integer of 2-12.

Another embodiment of the present invention provides an epoxy cured product, which is obtained by performing a curing reaction on the aforementioned self-curable epoxy resin composition.

Therefore, the self-curable epoxy resin composition of the present invention is formed by using renewable materials to synthesize epoxy resin, and then combined with a nitrogen-containing catalyst to avoid the use of a curing agent to cause high levels in the subsequent curing of the epoxy resin. The polar secondary alcohol makes the epoxy cured product have the characteristics of low dielectric constant and low dielectric loss.

100: Preparation method of self-curing epoxy resin composition

110, 120, 130, 140: steps

In order to make the above and other objects, features, advantages and embodiments of the present invention more comprehensible, the description of the accompanying drawings is as follows: Figure 1 shows a self-curing epoxy according to one embodiment of the present invention The step flow chart of the preparation method of the resin composition; Figure 2 shows the synthesis example 5 and synthesis example 7 with or without catalyst catalysis Thermal analysis diagram; Figure 3A shows the Fourier infrared spectrogram of each heating stage of Example 1; Figure 3B shows the Fourier infrared spectrum of each heating stage of Example 2; and Figure 4 shows the implementation The reaction mechanism diagram of the self-curing reaction in Example 1.

The various embodiments of the present invention will be discussed in more detail below. However, this embodiment can be an application of various inventive concepts and can be implemented in various specific ranges. The specific implementation is for illustrative purposes only, and is not limited to the scope of disclosure.

<Self-curing epoxy resin composition>

其中R¹為式(i)、式(ii)、式(iii)或式(iv)所示之一結構：

R²為氫、碳數1至6的烷基、碳數1至6的氧烷基或苯基，n為1至4的整數，m為2至12的整數；當n為2時，R¹為式(i)、式(ii)或式(iii)所示之結構，當n為3時，R¹為式(iv)所示之結構。 The present invention provides a self-curable epoxy resin composition comprising a nitrogen-containing catalyst and an epoxy resin, wherein the epoxy resin has a structure as shown in formula (I) or formula (II):

Where R ¹ is one of the structures shown in formula (i), formula (ii), formula (iii) or formula (iv):

R ² is hydrogen, an alkyl group having 1 to 6 carbons, an oxyalkyl group having 1 to 6 carbons, or a phenyl group, n is an integer from 1 to 4, and m is an integer from 2 to 12; when n is 2, R ¹ is the structure represented by formula (i), formula (ii) or formula (iii), when n is 3, R ¹ is the structure represented by formula (iv).

The nitrogen-containing catalyst is selected from a group consisting of 4-Dimethylaminopyridine (DMAP), imidazole and 2-methylimidazole (2-methylimidazole). Preferably, the present invention The embodiment is selected from dimethyl diazopyridine (DMAP) as the nitrogen-containing catalyst, and the nitrogen-containing catalyst may contain unshared electron pairs, which can interact with the epoxy group of the epoxy resin to facilitate initiation Subsequent curing reaction. Specifically, the content of the nitrogen-containing catalyst is 0.1 wt% to 2.0 wt%.

For example, when the epoxy resin composition has a structure of formula (I) and n is 2, R ¹ is a structure represented by formula (i), formula (ii) or formula (iii) and R ² is methoxy Group, which may have a structure as shown in formula (I-1), formula (I-2), formula (I-3) or formula (I-4); and when n is 3, R ¹ is the formula The structure shown in (iv) and R ² is a methoxy group, which may have a structure shown in formula (I-5):

其中m為2至12的整數。

Where m is an integer from 2 to 12.

In addition, when the epoxy resin composition has a structure of formula (II) and n is 2, R ¹ is a structure represented by formula (i), formula (ii) or formula (iii) and R ² is a methoxy group, It may have a structure as shown in formula (II-1), formula (II-2), formula (II-3) or formula (II-4); and when n is 3, R ¹ is formula (iv ) And R ² is a methoxy group, which can have a structure as shown in formula (II-5):

其中m為2至12的整數。

Where m is an integer from 2 to 12.

Thereby, the epoxy resin in the self-curable epoxy resin composition of the present invention can be cross-linked and cured under the catalysis of a nitrogen-containing catalyst, and no high-polarity secondary alcohol is produced during the curing process. The prepared epoxy cured product has excellent low dielectric loss and is suitable for semiconductor materials. For example, it can be used as a copper foil substrate in the semiconductor manufacturing process, especially as a copper foil substrate for multilayer metal interconnections.

<Preparation method of self-curing epoxy resin composition>

Please refer to FIG. 1. FIG. 1 is a flowchart of a method 100 for preparing a self-curing epoxy resin composition according to an embodiment of the present invention. The preparation method 100 of the self-curable epoxy resin composition includes step 110, step 120, step 130, and step 140.

其中R²為氫、碳數1至6的烷基、碳數1至6的氧烷基或苯基。依照本發明之實施例，所述之酚類化合物可為丁香酚(eugenol)或異丁香酚(isoeugenol)，且R²為甲氧基。 Step 110 is to provide a renewable raw material, which may be a phenolic compound, the phenolic compound having a structure as shown in formula (a1) or formula (a2):

Wherein R ² is hydrogen, an alkyl group having 1 to 6 carbons, an oxyalkyl group having 1 to 6 carbons, or a phenyl group. According to an embodiment of the present invention, the phenolic compound can be eugenol or isoeugenol, and R ² is a methoxy group.

其中R¹為式(i)、式(ii)、式(iii)或式(iv)所示之一結構：

m為2至12的整數。具體來說，所述醯氯化合物可為但不限於雙官能醯氯或三官能醯氯，依照本發明之實施例，所述之醯氯化合物為間苯二醯氯或1,3,5-苯三甲醯氯，當醯氯化合物為間苯二醯氯時，R¹為式(ii)所示之結構，而當醯氯化合物為1,3,5-苯三甲醯氯時，R¹為式(iv)所示之結構。 Step 120 is an esterification reaction step, which is to react a phenolic compound with a chlorinated compound to form an active ester-containing acrylic compound, wherein the chlorinated compound has one of formula (b1) or formula (b2) structure:

Where R ¹ is one of the structures shown in formula (i), formula (ii), formula (iii) or formula (iv):

m is an integer from 2 to 12. Specifically, the chlorinated compound may be, but not limited to, difunctional chlorinated or trifunctional chlorinated. According to the embodiment of the present invention, the chlorinated compound is isophthalic acid or 1,3,5- Trimethylbenzene chloride, when the chlorine compound is isophthalic acid chloride, R ¹ is the structure shown in formula (ii), and when the chlorine compound is 1,3,5-benzenetrimethic acid chloride, R ¹ is The structure shown in formula (iv).

其中R¹為式(i)、式(ii)、式(iii)或式(iv)所示之一結構：

R²為氫、碳數1至6的烷基、碳數1至6的氧烷基或苯基，n為1至4的整數，m為2至12的整數；當n為2時，R¹為式(i)、式(ii)或式(iii)所示之結構，當n為3時，R¹為式(iv)所示之結構。 The active ester-containing propenyl compound has a structure as one of formula (1) or formula (2):

Where R ¹ is one of the structures shown in formula (i), formula (ii), formula (iii) or formula (iv):

R ² is hydrogen, an alkyl group having 1 to 6 carbons, an oxyalkyl group having 1 to 6 carbons, or a phenyl group, n is an integer from 1 to 4, and m is an integer from 2 to 12; when n is 2, R ¹ is the structure represented by formula (i), formula (ii) or formula (iii), when n is 3, R ¹ is the structure represented by formula (iv).

Specifically, when the phenolic compound of formula (a1) reacts with the difunctional chlorin of formula (b1) and is catalyzed by triethylamine, the active ester-containing acrylic compound of formula (1) is formed, and wherein The phenolic compound of formula (a1) is eugenol, and the bifunctional chlorin of formula (b1) is isophthalic dichloride. Therefore, the acrylic compound containing active ester of formula (1) (hereinafter referred to as IPEU) is obtained. Is 2, R ¹ is the structure of formula (ii), and R ² is methoxy. In addition, the difunctional chlorin of formula (b1) in the above reaction is replaced with the trifunctional chlorin of formula (b2), and the trifunctional chlorin is 1,3,5-benzenetrimethylchloride, and the resulting formula (1) For the active ester-containing propenyl compound (hereinafter referred to as BTEU), n is 3, R ¹ is a structure of formula (iv), and R ² is a methoxy group.

When the phenolic compound of formula (a2) reacts with the difunctional chlorin of formula (b1) and is catalyzed by triethylamine, the active ester-containing acrylic compound of formula (2) is formed, and the formula (a2) The phenolic compound of the formula (b1) is isoeugenol, and the bifunctional chlorin of formula (b1) is isophthalic acid chloride. Therefore, the acrylic compound containing active ester (hereinafter referred to as IPIEU) of formula (2) is obtained, and n is 2 , R ¹ is the structure of formula (ii), and R ² is methoxy. In addition, the difunctional chlorin of formula (b1) in the above reaction is replaced with the trifunctional chlorin of formula (b2), and the trifunctional chlorin is 1,3,5-benzenetrimethylchloride, and the resulting formula (2) The active ester-containing propenyl compound (hereinafter referred to as BTIEU), where n is 3, R ¹ is the structure of formula (iv), and R ² is methoxy.

Step 130 is an epoxidation reaction step, which is to react the acrylic compound containing active ester with a metachloroperoxybenzoic acid (mCPBA) to epoxidize the double bond at the end of the acrylic compound containing active ester to form epoxy Resin, so that the epoxy resin also has an active ester structure. The epoxy resin has a structure as shown in formula (I-1), formula (I-2), formula (I-3), formula (I-4) or formula (I-5):

其中m為2至12的整數。

Where m is an integer from 2 to 12.

Specifically, when IPEU reacts with m-chloroperoxybenzoic acid, an epoxy resin of formula (I-2) (hereinafter referred to as IPEU-EP) is formed, and when BTEU reacts with m-chloroperoxybenzoic acid, then It will form an epoxy resin of formula (I-5) (hereinafter referred to as BTEU-EP).

In addition, the epoxy resin also has a structure as shown in formula (II-1), formula (II-2), formula (II-3), formula (II-4) or formula (II-5):

其中m為2至12的整數。

Where m is an integer from 2 to 12.

Specifically, when IPIEU reacts with m-chloroperoxybenzoic acid, an epoxy resin of formula (II-2) (hereinafter referred to as IPIEU-EP) is formed, and when BTIEU reacts with m-chloroperoxybenzoic acid, then It will form an epoxy resin of formula (II-5) (hereinafter referred to as BTIEU-EP).

Step 140 is a catalyzing step in which epoxy resin is added to a nitrogen-containing catalyst to form the self-curable epoxy resin composition. Specifically, the epoxy resin IPEU-EP, BTEU-EP and the nitrogen-containing catalyst can form a precursor solution containing a self-curing composition. For details of the nitrogen-containing catalyst, please refer to the foregoing, and will not be repeated here. Specifically, the epoxy resin IPEU-EP and BTEU-EP can be cross-linked under the catalysis of a nitrogen-containing catalyst by heating the precursor solution, and the heating curing temperature can be 120°C to 240°C, and the heating time can be 1 hour to 6 hours to form a self-curing epoxy resin composition (hereinafter referred to as SC-IPEU-EP and SC-BTEU-EP). More specifically, the foregoing heating method may adopt a multi-stage heating and curing method to heat the precursor solution, for example, at 120°C, 180°C, and 200°C. And heating at 220°C for 2 hours each. Regarding the added curing temperature and heating time can be flexibly adjusted according to the type of epoxy resin used, the present invention is not limited to this.

The present invention further provides an epoxy cured product, which is obtained by a curing reaction of the aforementioned self-curable epoxy resin composition, and the aforementioned curing reaction refers to the self-curable epoxy resin composition of Figure 1 The preparation method 100 of, will not be repeated here.

The following specific examples are used to further illustrate the present invention, so as to facilitate those skilled in the art to which the present invention pertains to fully utilize and practice the present invention without excessive interpretation. These embodiments should not be regarded as It limits the scope of the present invention, but is used to illustrate how to implement the materials and methods of the present invention.

<Synthesis example>

Synthesis Example 1. Synthesis of IPEU: 16.19g (98.6mmole) of eugenol, 9.98g (98.6mmole) of triethylamine and 200mL of dichloromethane were added to a 500mL glass reactor, and nitrogen gas and condenser were introduced. Dissolve 10.00 g (49.3 mmole) of isophthalic dichloride in 100 mL of dichloromethane, slowly drip it at 3~5°C for 1 hour, and then stir at 25°C for 12 hours. After the reaction, the salts were filtered out, and the dichloromethane was removed by distillation under reduced pressure. The precipitated solid was washed several times with a mixed solvent of methanol/water (1/4) and dried under vacuum at 60°C to obtain a white solid . ¹ H-NMR spectrum (ppm, CDCl ₃ ): δ=3.4 (4H, H ⁸ ), 3.8 (6H, H ¹³ ), 5.1 (4H, H ¹⁰ ), 5.9 (2H, H ⁹ ), 6.8 (4H, H ⁶ , H ¹¹ ), 7.1 (2H, H ⁵ ), 7.6 (1H, H ¹⁵ ), 8.4 (2H, H ¹⁴ ), 9.0 (1H, H ¹ ). The reaction equation of Synthesis Example 1 is shown in Table 1 below.

Synthesis Example 2. Synthesis of IPIEU: In a 500mL glass reactor, 16.19g (98.6mmole) of isoeugenol, 9.98g (98.6mmole) of triethylamine and 200mL of dichloromethane were added, and nitrogen and condenser were introduced. Then, 10.00 g (49.3 mmole) of isophthalic acid chloride was dissolved in 100 mL of dichloromethane, and slowly dripped at 3~5°C for 1 hour, and then heated to 25°C and stirred for 12 hours. After the reaction, the salts were filtered out, and the dichloromethane was removed by distillation under reduced pressure. The precipitated solid was washed several times with a mixed solvent of methanol/water (1/4) and dried under vacuum at 60°C to obtain a white solid . ¹ H-NMR spectrum (ppm, CDCl ₃ ): δ=3.4(4H), 3.8(6H ¹³ ), 5.1(4H, H ¹⁰ ), 5.9(2H, H ⁹ ), 6.8(4H, H ⁶ , H ¹¹ ), 7.1 (2H, H ⁵ ), 7.6 (1H, H ¹⁵ ), 8.4 (2H, H ¹⁴ ), 9.0 (1H, H ¹ ). The reaction equation of Synthesis Example 2 is shown in Table 2 below.

Synthesis Example 3. Synthesis of BTEU: Add 18.57g (113.1mmole) of eugenol, 11.44g (113.1mmole) of triethylamine, and 200mL of dichloromethane into a 500mL glass reactor, and pass nitrogen and condenser into the reactor. Dissolve 10.00g (37.7mmole) of 1,3,5 trimellityl chloride in 100mL of dichloromethane, and slowly drip it at 3~5℃ for 1 hour, and then stir at 25℃ for 12 hours . After the reaction, the salts were filtered out, and the dichloromethane was removed by distillation under reduced pressure. The precipitated solid was washed several times with a mixed solvent of methanol/water (1/4) and dried under vacuum at 60°C to obtain a pale yellow solid. ¹ H-NMR spectrum (ppm, CDCl ₃ ): δ=3.4 (6H, H ⁸ ), 3.8 (9H, H ¹³ ), 5.1 (6H, H ¹⁰ ), 5.9 (3H, H ⁹ ), 6.8 (6H, H ⁶ , H ¹¹ ), 7.1 (3H, H ⁵ ), 9.2 (3H, H ¹ ). The reaction equation of Synthesis Example 3 is shown in Table 3 below.

Synthesis Example 4. Synthesis of BTIEU: In a 500mL glass reactor, 18.57g (113.1mmole) of isoeugenol, 11.44g (113.1mmole) of triethylamine and 200mL of dichloromethane were added, and nitrogen and condenser were introduced. Then, 10.00g (37.7mmole) of 1,3,5 trimellityl chloride was dissolved in 100mL of dichloromethane, and slowly dripped at 3~5℃ for 1 hour, and then heated to 25℃ and stirred for 12 hour. After the reaction, the salts were filtered out, and the dichloromethane was removed by distillation under reduced pressure. The precipitated solid was washed several times with a mixed solvent of methanol/water (1/4) and dried under vacuum at 60°C to obtain a pale yellow solid. ¹ H-NMR spectrum (ppm, CDCl ₃ ): δ=3.4 (6H, H ⁸ ), 3.8 (9H, H ¹³ ), 5.1 (6H, H ¹⁰ ), 5.9 (3H, H ⁹ ), 6.8 (6H, H ⁶ , H ¹¹ ), 7.1 (3H, H ⁵ ), 9.2 (3H, H ¹ ).

The reaction equation of Synthesis Example 4 is shown in Table 4 below.

Synthesis Example 5. Synthesis of IPEU-EP: In a 500mL glass reactor, 10.00g (21.8mmole) of IPEU and 200mL of dichloromethane were added, and nitrogen and condenser were introduced, and m-chlorine was added at 0℃. Oxybenzoic acid 18.81g (109mmole), after it is completely dissolved, the temperature is raised to 40°C and reacted for 12 hours. After the reaction, the insoluble matter was filtered, and the filtrate was extracted with 10wt% sodium sulfate (Na ₂ SO ₃ ) several times until the water layer became transparent. After removing the organic layer, magnesium sulfate was added to remove water, and the filtrate was filtered and concentrated under reduced pressure. Dichloromethane was removed to obtain yellow powder. ¹ H-NMR spectrum (ppm, CDCl ₃ ): δ=2.5,2.8(4H,H ¹⁰ ),2.9(4H,H ⁸ ),3.2(2H,H ⁹ ),3.8(6H,H ¹³ ),6.8( 2H, H ⁶ ), 6.9 (2H, H ¹¹ ), 7.1 (2H, H ⁵ ), 7.6 (1H, H ¹⁵ ), 8.4 (4H, H ¹⁴ ), 9.0 (1H, H ¹ ). The reaction equation of Synthesis Example 5 is shown in Table 5 below.

Synthesis Example 6. Synthesis of IPIEU-EP: Add 10.00g (21.8mmole) of IPIEU and 200mL of dichloromethane into a 500mL glass reactor, and pass nitrogen and condenser into it, and add m-chlorine under the condition of 0℃. Oxybenzoic acid 18.81g (109mmole), after it is completely dissolved, the temperature is raised to 40°C and reacted for 12 hours. After the reaction, the insoluble matter was filtered, and the filtrate was extracted with 10wt% sodium sulfate (Na ₂ SO ₃ ) several times until the water layer became transparent. After removing the organic layer, magnesium sulfate was added to remove water, and the filtrate was filtered and concentrated under reduced pressure. Dichloromethane was removed to obtain yellow powder. ¹ H-NMR spectrum (ppm, CDCl ₃ ): δ=1.3 (6H, H ⁶ ), 3.1 (2H, H ⁵ ), 3.7 (2H, H ⁴ ), 3.7 (6H, H ⁸ ), 6.9, 7.0, 7.2 (6H, H ² , H ³ , H ⁷ ), 7.8 (1H, H ¹⁰ ), 8.4 (2H, H ⁹ ), 8.7 (1H, H ¹ ). The reaction equation of Synthesis Example 6 is shown in Table 6 below.

Synthesis Example 7. Synthesis of BTEU-EP: In a 500mL glass reactor, 10.00g (15.4mmole) of BTEU and 200mL of dichloromethane were added, and nitrogen and condenser were introduced, and meta-chlorine was added at 0℃. Oxybenzoic acid 19.96g (115.7mmole), after it is completely dissolved, the temperature is raised to 40°C and reacted for 12 hours. After the reaction, the insoluble matter was filtered, and the filtrate was extracted with 10wt% sodium sulfate (Na ₂ SO ₃ ) several times until the water layer became transparent. After removing the organic layer, magnesium sulfate was added to remove water, and the filtrate was filtered and concentrated under reduced pressure. Dichloromethane was removed to obtain yellow powder. ¹ H-NMR spectrum (ppm, CDCl ₃ ): δ=2.5,2.8(6H,H ¹⁰ ),2.9(6H,H ⁸ ),3.2(3H,H ⁹ ),3.8(9H,H ¹³ ),6.8( 3H, H ⁶ ), 6.9 (3H, H ¹¹ ), 7.1 (3H, H ⁵ ), 9.2 (3H, H ¹ ). The reaction equation of Synthesis Example 7 is shown in Table 7 below.

Synthesis Example 8. Synthesis of BTIEU-EP: In a 500mL glass reactor, 10.00g (21.8mmole) of BTIEU and 200mL of dichloromethane were added, and nitrogen gas and condenser were introduced, and meta-chlorine was added at 0℃. Oxybenzoic acid 18.81g (109mmole), after it is completely dissolved, the temperature is raised to 40°C and reacted for 12 hours. After the reaction, the insoluble matter was filtered, and the filtrate was extracted with 10wt% sodium sulfate (Na ₂ SO ₃ ) several times until the water layer became transparent. After removing the organic layer, magnesium sulfate was added to remove water, and the filtrate was filtered and concentrated under reduced pressure. Dichloromethane was removed to obtain yellow powder. ¹ H-NMR spectrum (ppm, CDCl ₃ ): δ=1.3 (9H, H ¹ ), 3.1 (3H, H ⁹ ), 3.7 (3H, H ⁸ ), 3.7 (9H, H ⁵ ), 6.9, 7.0, 7.2 (9H, H ⁶ , H ¹¹ , H ¹² ), 7.9 (3H, H ¹ ). The reaction equation of Synthesis Example 8 is shown in Table 8 below.

<Examples and Comparative Examples>

Example 1. Preparation of self-curing epoxy resin composition (hereinafter referred to as SC-IPEU-EP) by solvent method: Add IPEU-EP to dimethyldiaminopyridine and dissolve in dimethylformamide (Dimethylformamide) In the process, a precursor solution with a solid content of 30% is formed, and then the solution is coated on the glass using a glass coater. The temperature is raised to 80°C for 12 hours to remove most of the solvent, and then the solution is heated at 120°C under nitrogen. , 180 ℃, 200 ℃ and 220 ℃ each 2 hours stage heating and curing to obtain SC-IPEU-EP.

Example 2. Preparation of self-curable epoxy resin composition (hereinafter referred to as SC-BTEU-EP) by solvent method: adding BTEU-EP to dimethyl Diaminopyridine is dissolved in dimethylformamide to form a precursor solution with a solid content of 30%, and then the solution is coated on the glass using a glass coater, and the temperature is gradually raised to 80°C for 12 hours of heat treatment to remove the bulk Part of the solvent was then cured under nitrogen at 120°C, 180°C, 200°C, and 220°C for 2 hours each to obtain SC-BTEU-EP.

Comparative example 1. Preparation of epoxy resin cured by diaminodiphenylmethane (hereinafter referred to as IPEU-EP/DDM): Dissolve equivalent amounts of diaminodiphenyl methane and IPEU-EP in dimethylformamide In the process, a precursor solution with a solid content of 30% is formed, and then the solution is coated on the glass using a glass coater. The temperature is raised to 80°C for 12 hours to remove most of the solvent, and then the solution is heated at 120°C under nitrogen. , 180 ℃, 200 ℃ and 220 ℃ each 2 hours stage heating and curing to obtain IPEU-EP/DDM The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 uses diaminodiphenylmethane as the curing agent of the epoxy resin.

Comparative Example 2. Preparation of epoxy resin cured by diaminodiphenylmethane (hereinafter referred to as BTEU-EP/DDM): Dissolve equivalent amounts of diaminodiphenylmethane and BTEU-EP in dimethylformamide to form a solid Precursor solution with a content of 30%, then use a glass coater to coat the solution on the glass, gradually increase the temperature to 80°C for 12 hours heat treatment to remove most of the solvent, and then under nitrogen at 120°C, 180°C, 200 ℃ and 220 ℃ each 2 hours of heating and curing to obtain BTEU-EP/DDM. The difference between Comparative Example 2 and Example 2 is that Comparative Example 2 uses diaminodiphenylmethane as the curing agent of the epoxy resin.

<Thermal quality measurement of self-curing epoxy resin composition>

Example 1, Example 2, Comparative Example 1, and Comparative Example 2 were evaluated for thermal properties and dielectric properties. The thermal property evaluations included glass transition temperature (Tg), 5% thermogravimetric loss temperature (T _d5% ), and The residual rate of coke, the dielectric capacity, including the dielectric constant and dielectric loss, are evaluated as follows.

(1) Glass transition temperature: use a dynamic mechanical analyzer (Dynamic Mechanical Analyzer, DMA; model: Perkin-Elmer Pyris Diamond) to measure the storage modulus (Storage Modulus) of the cured product sample and the relationship between the Tan delta curve and temperature and the glass transfer temperature. In addition, thermo-mechanical analysis (Thermo-Mechanical Analysis, TMA) is used to measure the glass transition temperature. The conditions of the thermo-mechanical analysis are measured at a heating rate of 5°C/min.

(2) 5% thermogravimetric loss temperature and coke residual rate: Thermo-Gravimetric Analysis (TGA) is used to measure the 5% thermogravimetric loss temperature and the char yield of the sample at 800°C. The condition of thermogravimetric analysis is to measure the weight change of the sample using a thermogravimetric analyzer (model: Perkin-Elmer Pyrisl) at a heating rate of 20°C/min under a nitrogen atmosphere. The 5% thermogravimetric loss temperature refers to the temperature at which the weight loss of the cured product sample reaches 5%. The higher the 5% thermogravimetric loss temperature, the better the thermal stability of the sample. The coke residual ratio at 800°C refers to the residual weight ratio of the sample when the heating temperature reaches 800°C. The higher the residual weight ratio at 800°C, the better the thermal stability of the sample.

(3) Dielectric constant and dielectric loss: Use Agilent dielectric analyzer (Agilent; model: E4991A) to measure the dielectric constant and dielectric loss of the sample at 25°C and 1G Hz. The measurement results are shown in Table 9 below:

It can be seen from the results in Table 9 that when the dynamic mechanical analysis method is used for measurement, the glass transition temperature of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 are all higher than 180°C, and in the test of thermogravimetric analysis Among them, the 5% thermogravimetric loss temperatures of Example 1 and Example 2 are 374°C and 373°C, and the coke residual rate at 800°C is 29-40%, indicating that Example 1 and Example 2 have extremely excellent thermal stability Sex.

Then, the dielectric analysis results show that the dielectric constant and dielectric loss of Example 1 and Example 2 are lower than those of Comparative Example 1 and Comparative Example 2. From this, it can be seen that Example 1 and Example 2 of the present invention The self-curing epoxy resin composition does have the characteristics of low dielectric constant and low dielectric loss.

Please refer to Figure 2, which shows the thermal analysis diagrams of Synthesis Example 5 and Synthesis Example 7 with or without catalyst catalysis. From the results in Figure 2, it can be seen that the exothermic peak of the active ester and epoxy group in Synthesis Example 5 Is 305℃ (enthalpy is about 240 J/g), but containing 0.5wt% dimethyldiaminopyridine catalyzed Synthesis Example 5 (Example 1), its exothermic peak dropped to 166°C (enthalpy about 263 J/g). The exothermic peak of the reaction between the active ester and the epoxy group in Synthesis Example 7 is 224°C (the enthalpy is about 226J/g), but the synthesis example 7 (Example 2) catalyzed by 0.5wt% dimethyldiaminopyridine is exothermic The peak drops to 183°C (the enthalpy is about 258J/g). The above results show that the nitrogen-containing catalyst dimethyldiaminopyridine is an effective catalyst for the reaction of active esters and epoxy groups.

Please refer to Figure 3A and Figure 3B. Figure 3A shows the Fourier infrared spectrogram of each heating stage of Example 1, and Figure 3B shows the Fourier infrared spectrum of each heating stage of Example 2. the results of FIG. 3A and FIG. 3B is visible as the curing temperature increases (from room temperature to 240 deg.] C), for IPEU-EP, an ester group absorption peak of 1739cm ^-1 decreased from before curing 1726cm ^-1, while for BTEU -EP, the absorption peak of its ester group decreased from 1746cm ^-1 before hardening to 1730cm ^-1 . According to the principle of infrared light absorption, the absorption peak of aromatic ester group (Ar-OC(=O)-) is higher than that of fatty ester group (ROC(=O)-), so it can be proved that the implementation of the Changes in the structure of the ester group in Example 1 and Example 2.

Based on the results of Fig. 2, Fig. 3A and Fig. 3B, the self-curing reaction mechanism of the self-curing epoxy resin composition of the present invention can be inferred, as shown in Fig. 4, which is shown in Fig. 4 The reaction mechanism diagram of the self-curing reaction in Example 1, which includes step 1 to step 4. Step 1: Dimethyldiaminopyridine attacks the epoxy group to form intermediate (I) with alkyl anion, Step 2: The alkyl anion of intermediate (I) and active ester group form a complex, Step 3: Intermediate (I) The alkyl anion attacks the active ester group to form an intermediate (II) and phenolic anion, step 4: phenolic anion attacks intermediate (II) to form intermediate (III), and release dimethyldiaminopyridine, then repeat the step for dimethyldiaminopyridine 1 Attack the epoxy group.

From the results in Figure 4, it can be seen that in the self-curing reaction mechanism of the self-curing epoxy resin composition described above, no polar secondary alcohol is produced, which helps to reduce the epoxy cured product. Dielectric constant.

In summary, according to the self-curable epoxy resin composition of the present invention, it can be cured by cross-linking with the epoxy resin under the catalysis of a nitrogen-containing catalyst, and can avoid high polarity during the curing process. The secondary alcohol has excellent thermal properties, that is, high glass transition temperature and thermal stability, and can further improve the dielectric capacity, which is beneficial to the application of electrical materials.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone familiar with the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection of the present invention The scope shall be subject to those defined in the attached patent scope.

100: Preparation method of self-curing epoxy resin composition

110, 120, 130, 140: steps

Claims (10)

A self-curable epoxy resin composition, comprising: a nitrogen-containing catalyst, wherein the nitrogen-containing catalyst is selected from the group consisting of dimethyldiaminopyridine, imidazole and dimethylimidazole; and Epoxy resin, the epoxy resin has a structure as shown in formula (I) or formula (II):

Where R ¹ is one of the structures shown in formula (i), formula (ii), formula (iii) or formula (iv):

R ² is hydrogen, an alkyl group having 1 to 6 carbons, an oxyalkyl group having 1 to 6 carbons, or a phenyl group, n is an integer from 1 to 4, m is an integer from 2 to 12, and when n is 2, R ¹ is the structure represented by formula (i), formula (ii) or formula (iii), when n is 3, R ¹ is the structure represented by formula (iv). According to the self-curable epoxy resin composition described in item 1 of the scope of the patent application, the content of the nitrogen-containing catalyst is 0.1 wt% to 2.0 wt%. The self-curable epoxy resin composition described in item 1 of the scope of the patent application, wherein the epoxy resin has the formula (I-1), the formula (I-2), the formula (I-3), the formula ( I-4), Formula (I-5), Formula (II-1), Formula (II-2), Formula (II-3), Formula (II-4), or Formula (II-5) structure:

Where m is an integer from 2 to 12. A method for preparing a self-curing epoxy resin composition as described in item 1 of the scope of the patent application, comprising: providing a renewable raw material, which is a phenolic compound; An esterification reaction step is carried out to react the phenolic compound with a chlorine compound to form an active ester-containing acrylic compound; an epoxidation reaction step is carried out to make the active ester-containing acrylic compound and a chlorine perchlorate Oxybenzoic acid reacts to epoxidize the double bond at the end of the acrylic compound containing the active ester to form an epoxy resin; and a catalytic step is performed to add the epoxy resin to a nitrogen-containing catalyst to form The self-curable epoxy resin composition, wherein the nitrogen-containing catalyst is selected from a group consisting of dimethyldiazide pyridine, imidazole and dimethylimidazole. The method for preparing a self-curing epoxy resin composition as described in item 4 of the scope of patent application, wherein the phenolic compound has a structure as shown in formula (a1) or formula (a2):

Wherein R ² is hydrogen, an alkyl group having 1 to 6 carbons, an oxyalkyl group having 1 to 6 carbons, or a phenyl group. The method for preparing a self-curing epoxy resin composition as described in item 4 of the scope of patent application, wherein the chlorinated compound has a structure shown in formula (b1) or formula (b2):

Where R ¹ is one of the structures shown in formula (i), formula (ii), formula (iii) or formula (iv):

m is an integer from 2 to 12. The method for preparing a self-curing epoxy resin composition as described in item 4 of the scope of patent application, wherein the active ester-containing acrylic compound has a structure as one of formula (1) or formula (2):

Where R ¹ is one of the structures shown in formula (i), formula (ii), formula (iii) or formula (iv):

R ² is hydrogen, an alkyl group having 1 to 6 carbons, an oxyalkyl group having 1 to 6 carbons, or a phenyl group, n is an integer from 1 to 4, m is an integer from 2 to 12, and when n is 2, R ¹ is the structure represented by formula (i), formula (ii) or formula (iii), when n is 3, R ¹ is the structure represented by formula (iv). According to the method for preparing a self-curing epoxy resin composition described in item 4 of the scope of the patent application, the content of the nitrogen-containing catalyst is 0.1 wt% to 2.0 wt%. The method for preparing a self-curable epoxy resin composition as described in item 4 of the scope of the patent application, wherein the epoxy resin has formula (I-1), formula (I-2), and formula (I-3) , Formula (I-4), Formula (I-5), Formula (II-1), Formula (II-2), Formula (II-3), Formula (II-4) or Formula (II-5) Show one structure:

Where m is an integer from 2 to 12. An epoxy cured product is obtained by a curing reaction of the self-curable epoxy resin composition described in any one of items 1 to 3 in the scope of the patent application.

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