Alkenyl bond-containing benzocyclobutene resin and method for producing same

Abstract

The present invention belongs to the technical field of high performance resins, and provides a method for preparing alkenyl bond-containing benzocyclobutene resin and other resins. The structural formula of the resin of the present invention is as follows, where R1, R2 and R3 are benzocyclobutene groups or hydrogen atoms, at least one of which is a benzocyclobutene group, R4, R5 and R6 are alkyl groups, vinyl groups or hydrogen atoms, and R4, R5 and R6 are the same. The preparation method is that unsaturated resins with different molecular weights and halogenated benzocyclobutenes can be prepared by Heck reaction. The preparation conditions of the benzocyclobutene resin are mild and easy to prepare, and the resin formed after the temperature is raised and ring-opening polymerization cured has high crosslink density, high heat resistance, good resin smoothness, extremely low dielectric constant and dielectric loss, and is an excellent photoelectric material. [Formula 1] JPEG2025501032000009.jpg22135

Description

[Technical field]

[0001] The present invention relates to the technical field of high performance resins, and more particularly to alkenyl bond-containing benzocyclobutene resins and methods for preparing the same. [Background technology]

[0002] Benzocyclobutene has a unique non-polar quaternary ring structure, so that under suitable temperature conditions, the quaternary ring can be opened, and the compound itself can undergo self-polymerization, thereby undergoing polymerization and curing reactions; it can also undergo Diels-Alder reaction with other olefin-containing functional groups, and then undergo polymerization and curing. The ring-opening polymerization and curing process of benzocyclobutene does not generate any small molecular compounds, and the cured product is easy to process, and has the advantages of excellent heat resistance, low thermal expansion coefficient, low moisture absorption, good flatness, good mechanical performance, extremely low dielectric constant and dielectric loss, etc. Benzocyclobutene resins are widely used in aerospace, microelectronic packaging, electrical insulation, photoresists and other fields.

[0003] Benzocyclobutene consists of only carbon and hydrogen elements and has a low dielectric constant after curing, but it is liquid at room temperature and is not easy to mold, so it is necessary to carry out a derivatization reaction to add other functional groups. Such resins are generally prepared by first synthesizing a benzocyclobutene derivative and then undergoing a prepolymerization reaction to obtain a prepolymer with a certain molecular weight, which then enables the molding process of the material. For example, the series of CYCLOTENE Advanced Electronics Resins photoresists developed by Dow Chemical Company are small molecular compounds produced by the Heck reaction of DVS (1,3-divinyltetramethyldisiloxane) and 4-bromobenzocyclobutene, which are then further subjected to a prepolymerization reaction. Therefore, the currently popular benzocyclobutene resins are relatively complicated to synthesize, have high production costs, and are difficult to popularize in application. Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to solve the existing problems in benzocyclobutene resins, such as complex synthesis processes, high production costs, and difficulty in widespread application, and to provide an alkenyl bond-containing benzocyclobutene resin with excellent performance and convenient production, as well as other production methods.

[0005] The first aspect of the present invention is the following formula I

Chemical formula

[0006] The structural formula of the benzocyclobutene group is the following formula

Chemical formula

[0007] The degree of polymerization of the benzocyclobutene resin is 0 < n < 5000, preferably 2 < n < 3000, more preferably 5 < n < 1000.

[0008] Another aspect of the present invention provides a method for producing an alkenyl bond-containing benzocyclobutene resin described in the first aspect of the present invention.

[0009] The method for producing the resin represented by formula I provided in the present invention includes the following steps:

[0010] An unsaturated resin, a halogenated benzocyclobutene, a catalyst, a ligand, an acid binder and a reaction solvent are reacted under heating and stirring in a nitrogen gas atmosphere, and the resulting reaction liquid is treated to obtain a benzocyclobutene resin.

[0011] The unsaturated resin described in the present invention may be any one of 1,2-polybutadiene and 1,2-polyisoprene, but is not limited thereto, and is preferably 1,2-polybutadiene; the 1,2-polybutadiene may be isotactic 1,2-polybutadiene or syndiotactic 1,2-polybutadiene, or may be a mixture of isotactic 1,2-polybutadiene and syndiotactic 1,2-polybutadiene, and is preferably a mixture of isotactic 1,2-polybutadiene and syndiotactic 1,2-polybutadiene, in which the content of isotactic 1,2-polybutadiene is more than 50%, and the average molecular weight of the polybutadiene is 100-100,000, preferably 200-50,000, more preferably 500-30,000.

[0012] The halogenated benzocyclobutene according to the present invention is one or a mixture of a plurality of 4-iodobenzocyclobutene, 4-bromobenzocyclobutene, and 4-chlorobenzocyclobutene, and is preferably 4-bromobenzocyclobutene. The weight ratio of the halogenated benzocyclobutene to the unsaturated resin is (0.1-10):1, and preferably (0.3-5):1.

[0013] The catalyst according to the present invention is a palladium salt, including but not limited to palladium acetate, palladium chloride, Pd / C, tetrakis(triphenylphosphine)palladium, and its dosage is 0.001-10.0% of the moles of halogenated benzocyclobutene; the ligand is triphenylphosphine or tri(o-methylphenyl)phosphine, and its dosage is 1-50 times the moles of the catalyst.

[0014] The acid-binding agent according to the present invention is an inorganic or organic base, including, but not limited to, any one of triethylamine, n-butylamine, pyridine, potassium carbonate, sodium carbonate, sodium acetate and potassium acetate, preferably triethylamine.

[0015] The solvent according to the present invention is any one of N,N-dimethylformamide, methanol, toluene, xylene, trimethylbenzene, acetonitrile, tetrahydrofuran, 1,4-dioxane, and preferably acetonitrile.

[0016] The reaction temperature for the heating and stirring of the present invention is room temperature to 150° C., preferably 70 to 100° C.; the stirring reaction time is 3 to 35 hours. The reaction solution is treated by adding the reaction solution to a non-polar solvent, filtering, washing with water until neutral, concentrating, and purifying (for example, separation and purification by column chromatography) to obtain a colorless or pale yellow transparent oily product.

[0017] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0018] (1) The resin of the present invention is prepared by reacting an unsaturated resin with a known molecular weight with 4-bromobenzocyclobutene. The molecular weight distribution of the product obtained after post-treatment is similar to that of the unsaturated resin in the raw material, and has relatively good uniformity (see FIG. 1). Therefore, no pre-polymerization reaction is required and the product can be directly used in the next process. At the same time, the desired target product can be prepared by selecting unsaturated resins with different molecular weights in the raw material as required. Unlike resins prepared by other methods, the resin prepared by the present invention does not require pre-polymerization reaction, which greatly reduces production costs. (2) The laminate made of the resin prepared in the present invention has a dielectric constant (Dk) of less than 2.50 and a dielectric loss (Df) of less than 0.001 when tested at a frequency of 10 GHz, and has excellent electrical performance, which is suitable for the requirements of high-speed and high-frequency PCBs and packaging materials. [Brief description of the drawings]

[0019] [Figure 1] FIG. 2 is a GPC detection diagram of the resin produced in Example 1 of the present invention.

[0020] [Diagram 2] FIG. 2 is an IR diagram of the resins produced in Examples 1 to 8 of the present invention.

[0021] [Diagram 3] IR diagrams of the resins produced in Examples 1, 3, 5, and 6 of the present invention after curing, respectively.

[0022] [Figure 4] FIG. 2 is a DSC diagram of the resin of Example 1 of the present invention.

[0023] [Diagram 5] FIG. 2 is a DSC diagram of the resin produced in Example 1 of the present invention after curing.

[0024] [Figure 6] 1 is an AFM image of a hardened thin plate in Example 1 of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] Hereinafter, the applicant will explain the technical solution of the present invention in detail based on specific embodiments.

[0026] Example 1 The method for producing the alkenyl bond-containing benzocyclobutene resin is as follows.

[0027] [ka]

[0028] In a three-neck flask, 101.6g (0.55mol) of 4-bromobenzocyclobutene, 150.0g of polybutadiene (Nippon Soda B-3000, average molecular weight 3200, 1,2-vinyl structure 90% or more), 113g (1.1mol) of triethylamine, 1.24g (5.5mmol) of palladium acetate, 5.06g (0.0167mol) of tris(o-tolyl)phosphine, and 500mL of acetonitrile were added in this order, and the mixture was reacted by heating under reflux for 24 hours under a nitrogen gas atmosphere. For the reaction principle, refer to the above formula. After the reaction, petroleum ether was added and stirred, filtered, washed with water until neutral, concentrated, and separated and purified by column chromatography to obtain 191g of a pale yellow transparent oil.

[0029] The alkenyl bond-containing benzocyclobutene resin obtained in this example was subjected to infrared spectrum analysis. The results are shown in FIG. 2, curve 1. -1 The peaks appearing at 1635, 1597, 1495, and 1448 cm are due to the C=CH, methylene, methine, and CH stretching vibrations on benzocyclobutene, respectively. -1 The peak appearing at 3070 cm was found to be a characteristic absorption peak of a benzene ring, indicating that the prepared resin contained benzocyclobutene. For the IR spectrum of the cured resin, see curve 1 in Figure 3. From this figure, -1 C=CH stretching vibration peak and 2841cm -1 It was found that the CH stretching vibration peak in benzocyclobutene disappeared, which explained that both the alkenyl bond and the four-membered ring in benzocyclobutene participated in the reaction during curing. The alkenyl bond-containing benzocyclobutene resin obtained in this example was detected by GPC, and Mp=4022 was found, as shown in FIG. 1; the alkenyl bond-containing benzocyclobutene resin obtained in this example was pressed into a thin plate (130×80 mm, ≦0.8 mm), and the flatness of the thin plate was very good. It was measured at a frequency of 10 GHz, and the measurement data was shown in Table 1 below. The glass transition temperature after the resin was cured exceeded 260° C. (see FIG. 5). The AFM image of the cured thin plate is shown in FIG. 6.

[0030] Example 2 The method for producing the alkenyl bond-containing benzocyclobutene resin is as follows.

[0031] In a three-neck flask, 152.4g (0.83mol) of 4-bromobenzocyclobutene, 150.0g of polybutadiene (Nippon Soda B-3000, average molecular weight 3200, 1,2-vinyl structure 90% or more), 169.5g (1.67mol) of triethylamine, 1.89g (8.4mmol) of palladium acetate, 7.72g (0.025mol) of tris(o-tolyl)phosphine, and 750mL of acetonitrile were added in this order, and reacted by heating under reflux for 24 hours under a nitrogen gas atmosphere. The reaction principle was the same as in Example 1 above, and after the reaction was completed, petroleum ether was added and stirred, filtered, washed with water until neutral, concentrated, and separated and purified by column chromatography to obtain 185.5g of a colorless transparent oil.

[0032] The alkenyl bond-containing benzocyclobutene resin obtained in this example was subjected to infrared spectrum analysis, and the results are shown in FIG. 2, curve 1. The AFM image of the cured thin plate obtained in this example is omitted because it is similar to FIG. 6.

[0033] Example 3 The method for producing the alkenyl bond-containing benzocyclobutene resin is as follows.

[0034] In a three-neck flask, 169.3 g (0.92 mol) of 4-bromobenzocyclobutene, 150.0 g of polybutadiene (manufactured by Shanghai Zhenjun Biotechnology Co., Ltd., average molecular weight 5000, 20% 1,2-vinyl structure, 30% cis-1,4-butadiene; 50% trans-1,4-butadiene), 255.5 g (1.85 mol) of potassium carbonate, 1.64 g (7.3 mmol) of palladium acetate, 8.44 g (0.028 mol) of tris(o-tolyl)phosphine, and 840 mL of DMF were added in this order, and the mixture was heated under a nitrogen gas atmosphere and reacted at 130°C for 12 hours. The reaction principle was the same as in Example 1 above. After the reaction was completed, petroleum ether was added and stirred, filtered, washed with water until neutral, concentrated, and separated and purified by column chromatography to obtain 230.0 g of a pale yellow transparent oil.

[0035] The alkenyl bond-containing benzocyclobutene resin obtained in this example was subjected to infrared spectrum analysis, and the test results are shown in curve 3 of FIG. 2, and the IR spectrum after the resin was cured is shown in curve 2 of FIG. 3. The AFM image of the cured thin plate obtained in this example is omitted because it is similar to FIG. 6. When compared with the IR spectrum before and after curing of the resin obtained in Example 1 of the present invention using polybutadiene with an average molecular weight of 3200 as a raw material, there was no obvious difference. The alkenyl bond-containing benzocyclobutene resin prepared in this example was cured to prepare a thin plate (130×80 mm, ≦0.8 mm), and the flatness of the thin plate was very good, measured at a frequency of 10 GHz, and the measurement data are shown in Table 1 below. There was no obvious difference compared to Example 1 of the present invention, and even when the molecular weight of the raw material polybutadiene used in this example was obviously large, a resin with good dielectric properties was obtained.

[0036] Example 4 The method for producing the alkenyl bond-containing benzocyclobutene resin is as follows.

[0037] In a three-neck flask, 507.8g (2.77mol) of 4-bromobenzocyclobutene, 150.0g of polybutadiene (manufactured by Shanghai Zhenjun Biotechnology Co., Ltd., average molecular weight 5000, 20% 1,2-vinyl structure, 30% cis-1,4-butadiene; 50% trans-1,4-butadiene), 561.3g (5.54mol) of triethylamine, 4.92g (0.022mol) of palladium acetate, 50.6g (0.167mol) of tris(o-tolyl)phosphine, and 2000mL of acetonitrile were added in this order, and reacted by heating under reflux for 24 hours under a nitrogen gas atmosphere. The reaction principle was the same as in Example 1 above, and after the reaction was completed, petroleum ether was added and stirred, filtered, washed with water until neutral, concentrated, and separated and purified by column chromatography to obtain 550g of a pale yellow transparent oil.

[0038] The alkenyl bond-containing benzocyclobutene resin obtained in this example was subjected to infrared spectrum analysis, and the results are shown in curve 4 of Figure 2. The AFM image of the cured thin plate obtained in this example is omitted because it is similar to Figure 6.

[0039] Example 5 The method for producing the alkenyl bond-containing benzocyclobutene resin is as follows.

[0040] [ka]

[0041] In a three-neck flask, 56.3g (0.31mol) of 4-bromobenzocyclobutene, 50.0g of polyisoprene (self-made, average molecular weight 3000, 1,2-polyisoprene content >40%), 49.5g (0.49mol) of triethylamine, 0.55g (2.4mmol) of palladium acetate, 2.23g (7.3mmol) of tris(o-tolyl)phosphine, and 350mL of acetonitrile were added in this order, and reacted under nitrogen gas atmosphere for 24 hours under reflux. The reaction principle is as shown in the above formula. After the reaction is completed, petroleum ether is added and stirred, filtered, washed with water until neutral, concentrated, and separated and purified by column chromatography to obtain 65g of a pale yellow transparent oil.

[0042] The alkenyl bond-containing benzocyclobutene resin obtained in this example was subjected to infrared spectrum analysis. The results are shown in FIG. 2, curve 5. -1 The peaks appearing in the 1635, 1597, 1495, and 1448 cm are due to the C=CH, methyl, methylene, and CH stretching vibrations of benzocyclobutene, respectively. -1 The peak appearing at 3070 cm was found to be a characteristic absorption peak of a benzene ring, indicating that the prepared resin contained benzocyclobutene; for the IR spectrum of the cured resin, refer to curve 3 in Figure 3. From this figure, -1 C=CH stretching vibration peak and 2841cm -1 It was found that the CH stretching vibration peak in benzocyclobutene disappeared, which explained that both the alkenyl bond and the four-membered ring in benzocyclobutene were involved in the reaction during curing. The alkenyl bond-containing benzocyclobutene resin obtained in this example was cured to prepare a thin plate (130 x 80 mm, ≦0.8 mm). The flatness of the thin plate was very good and was measured at a frequency of 10 GHz. The measurement data are shown in Table 1 below.

[0043] Example 6 The method for producing the alkenyl bond-containing benzocyclobutene resin is as follows.

[0044] In a three-neck flask, 56.3 g (0.24 mol) of 4-iodobenzocyclobutene, 50.0 g of polyisoprene (self-made, average molecular weight 5000, 1,2-polyisoprene content >40%), 67.7 g (0.49 mol) of potassium carbonate, 0.55 g (2.4 mmol) of palladium acetate, 2.23 g (7.3 mmol) of tris(o-tolyl)phosphine, and 350 mL of DMF were added in this order, and the mixture was heated to 130°C under a nitrogen gas atmosphere and reacted for 12 hours. The reaction principle was the same as in Example 5 above. After the reaction was completed, petroleum ether was added and stirred, filtered, washed with water until neutral, concentrated, and separated and purified by column chromatography to obtain 67.7 g of a pale yellow transparent oil.

[0045] The alkenyl bond-containing benzocyclobutene resin obtained in this example was subjected to infrared spectrum analysis, and the test results are shown in curve 6 of FIG. 2, and the IR spectrum after the resin was cured is shown in curve 4 of FIG. 3. The IR spectrum before and after curing of the resin obtained in Example 5 of the present invention using polyisoprene with an average molecular weight of 3000 as the raw material was compared with that of the resin obtained in Example 5 of the present invention, and no obvious difference was found. The alkenyl bond-containing benzocyclobutene resin prepared in this example was cured to prepare a thin plate (130×80 mm, ≦0.8 mm), and the flatness of the thin plate was very good, measured at a frequency of 10 GHz, and the measurement data are shown in Table 1 below.

[0046] Example 7 The method for producing the alkenyl bond-containing benzocyclobutene resin is as follows.

[0047] In a three-neck flask, 56.3 g (0.24 mol) of 4-iodobenzocyclobutene, 50.0 g of polyisoprene (self-made, average molecular weight 3000, 1,2-polyisoprene content >40%), 49.5 g (0.49 mol) of triethylamine, 0.43 g (2.4 mmol) of palladium chloride, 2.23 g (7.3 mmol) of tris(o-tolyl)phosphine, and 350 mL of DMF were added in this order, and the mixture was heated to 80°C under a nitrogen gas atmosphere and reacted for 16 hours. The reaction principle was the same as in Example 5 above. After the reaction was completed, petroleum ether was added and stirred, filtered, washed with water until neutral, concentrated, and separated and purified by column chromatography to obtain 60.2 g of a pale yellow transparent oil.

[0048] The alkenyl bond-containing benzocyclobutene resin obtained in this example was subjected to infrared spectrum analysis, and the test results were referred to curve 7 in FIG.

[0049] Example 8 The method for producing the alkenyl bond-containing benzocyclobutene resin is as follows.

[0050] In a three-neck flask, 42.3 g (0.23 mol) of 4-bromobenzocyclobutene, 50.0 g of polybutadiene (self-produced, average molecular weight 3000, 1,2-polyisoprene content >40%), 49.5 g (0.36 mol) of potassium carbonate, 0.52 g (2.3 mmol) of palladium acetate, 2.10 g (6.9 mmol) of tris(o-tolyl)phosphine, and 320 mL of DMF were added in this order, and the mixture was heated to about 150° C. under a nitrogen gas atmosphere and refluxed for 12 hours. The reaction principle was as described in Example 1 above. After the reaction was completed, petroleum ether was added, stirred, filtered, washed with water until neutral, concentrated, and separated and purified by column chromatography to obtain 58.6 g of a pale yellow transparent oil.

[0051] The alkenyl bond-containing benzocyclobutene resin obtained in this example was subjected to infrared spectrum analysis, and the test results are shown in curve 8 of FIG.

[0052] The resins produced in Examples 1 to 8 of the present invention were cured to prepare thin plates. The thin plates had excellent flatness and, when measured at a frequency of 10 GHz, had a dielectric constant (Dk) of less than 2.50 and a dielectric loss (Df) of less than 0.001, providing excellent electrical performance. At the same time, the glass transition temperature after curing was also higher, providing better dielectric performance than currently mainstream dielectric materials (see Comparative Examples 1 and 2 in Table 1 below, which are ODV resin and SEBS resin, respectively), and being more suitable for application to 5G and 6G high-speed and high-frequency electronic materials.

[0053] [Table 1]

Claims

1. An alkenyl bond-containing benzocyclobutene resin having the structural formula: 【Chemistry 1】 However, R １ , R ２ and R ３ is a benzocyclobutene group or a hydrogen atom, R １ , R ２ and R ３ At least one of R is a benzocyclobutene group; ４ , R ５ and R ６ is an alkyl group, a vinyl group, or a hydrogen atom, and R ４ , R ５ and R ６ is the same, 0<n<5000.

2. The alkenyl bond-containing benzocyclobutene resin according to claim 1, characterized in that n is in the range of 0<n<1000, preferably in the range of 2<n<200, and more preferably in the range of 5<n<100.

3. The method for producing an alkenyl bond-containing benzocyclobutene resin according to claim 1 or 2 is characterized by comprising the following steps: An unsaturated resin, a halogenated benzocyclobutene, a catalyst, a ligand, an acid binder and a reaction solvent are reacted under heating and stirring in a nitrogen gas atmosphere, and the resulting reaction liquid is treated to obtain an alkenyl bond-containing benzocyclobutene resin.

4. The unsaturated resin is an unsaturated polymer having an alkenyl bond in the chain, and includes, but is not limited to, 1,2-polybutadiene, 1,2-polyisoprene, The 1,2-polybutadiene is isotactic 1,2-polybutadiene or syndiotactic 1,2-polybutadiene, or a mixture of isotactic 1,2-polybutadiene and syndiotactic 1,2-polybutadiene; 4. The method for producing an alkenyl bond-containing benzocyclobutene resin according to claim 3, wherein the unsaturated resin has an average molecular weight of 100 to 100,000.

5. The halogenated benzocyclobutene is one or a mixture of 4-iodobenzocyclobutene, 4-bromobenzocyclobutene, and 4-chlorobenzocyclobutene; The method for producing an alkenyl bond-containing benzocyclobutene resin according to claim 3, wherein the weight ratio of the halogenated benzocyclobutene to the unsaturated resin is (0.1 to 10):

1.

6. The catalyst is a palladium salt, including but not limited to palladium acetate, palladium chloride, Pd / C, tetrakis(triphenylphosphine)palladium, and its dosage is 0.001-10.0% of the moles of halogenated benzocyclobutene; The method for producing an alkenyl bond-containing benzocyclobutene resin according to claim 3, wherein the ligand is triphenylphosphine or tri(o-methylphenyl)phosphine, and the amount of the ligand is 1 to 50 times the number of moles of the catalyst.

7. 4. The method for producing an alkenyl bond-containing benzocyclobutene resin according to claim 3, wherein the acid binder is an inorganic base or an organic base, including, but not limited to, any one of triethylamine, pyridine, potassium carbonate, sodium carbonate, sodium acetate, and potassium acetate.

8. The method for producing an alkenyl bond-containing benzocyclobutene resin according to claim 3, wherein the solvent is any one of N,N-dimethylformamide, methanol, toluene, xylene, trimethylbenzene, acetonitrile, tetrahydrofuran, and 1,4-dioxane.

9. The reaction temperature during the heating and stirring is room temperature to 150° C., preferably 70 to 100° C.

4. The method for producing an alkenyl bond-containing benzocyclobutene resin according to claim 3, wherein the reaction time of the stirring is 3 to 35 hours.

10. The method for producing an alkenyl bond-containing benzocyclobutene resin according to claim 3, characterized in that the reaction solution is treated by adding the reaction solution to a non-polar solvent, filtering the reaction solution, washing the solution with water until the solution becomes neutral, concentrating the solution, and isolating and purifying the solution by column chromatography to obtain a colorless or pale yellow transparent oily product.

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