A bismaleimide-polyether amine photocuring resin and a preparation method thereof

Abstract

The application provides a bismaleimide-polyether amine photocuring resin and a preparation method thereof. 100 parts of bismaleimide and 100-200 parts of polyether amine are pre-reacted, 0.001-5 parts of a catalyst, 0.001-1 parts of a polymerization inhibitor and 100-400 parts of glycidyl methacrylate are added to carry out grafting reaction, and the bismaleimide-polyether amine photocuring resin is obtained. The bismaleimide-polyether amine photocuring resin provided by the application has the characteristics of realizing photocuring through ultraviolet light irradiation on the basis of retaining the excellent thermal performance and good mechanical performance of traditional bismaleimide, and effectively solves the problem of poor forming performance. The method disclosed by the application has simple process and mild reaction conditions, is suitable for industrial production, and the prepared material has wide application potential in the fields of photocuring printing and electronic packaging.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a bismaleimide-polyetheramine photocurable resin and its preparation method. Background Technology

[0002] Bismaleimide (BMI) resin is a thermosetting polymer material that has attracted much attention due to its excellent dielectric properties, wave transmission, flame resistance, and mechanical strength. It is widely used in advanced resin-based composites, aerospace materials, insulating materials, wear-resistant coatings, and electronic packaging. Current research on BMI resin mainly focuses on optimizing its overall performance through molecular structure design. In terms of molecular modification, researchers have effectively reduced the crystallinity of the resin, broadened the processing window, and improved solubility and toughness by introducing flexible segments or large-volume side groups. Simultaneously, introducing functional groups such as phosphorus and silicon into the molecular chain can endow the resin with flame retardant and low dielectric properties to meet the stringent requirements of different application scenarios. Furthermore, by copolymerizing or blending with other resin systems such as epoxy resins and cyanate esters, complementary properties can be achieved, resulting in materials that combine heat resistance and good processability. Optimization of processing performance is another research focus. Addressing the issues of high melting point and high melt viscosity in traditional BMI resins, researchers have lowered the melting point through molecular structure design or added plasticizers to improve flowability. Curing processes have also been innovated. By developing novel curing agents and systems, low-temperature rapid curing has been achieved, improving production efficiency and making the manufacture of complex-shaped parts possible. Polyetheramines have received continuous attention in the toughening and modification research of thermosetting resins due to their moderate flexible chain segment length, low viscosity, and high reactivity of terminal amino groups. Their toughening mechanism is mainly based on the introduction of flexible polyether segments, which reduces the crosslinking density of the system and improves the molecular chain mobility. Simultaneously, the terminal amino groups participate in the curing reaction to form chemical bonds, achieving in-situ toughening. Summary of the Invention

[0003] In view of the limitations and shortcomings of existing technologies, the purpose of this invention is to provide a bismaleimide-polyetheramine photocurable resin and its preparation method. This invention involves grafting polyetheramine onto both sides of bismaleimide and introducing photosensitive groups, using chemical modification to toughen the bismaleimide resin, and verifying its feasibility in the field of photocuring.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] A method for preparing a bismaleimide-polyetheramine photocurable resin includes the following steps:

[0006] (1) Under nitrogen protection at a temperature of 50~100 ℃, 100 parts of bismaleimide were added to an organic solvent by molar, and then 100~200 parts of polyetheramine were slowly added dropwise, followed by 0.001~5 parts of catalyst. The reaction was carried out for 1~5 hours to obtain solution A.

[0007] (2) Under nitrogen protection at a temperature of 50~100 ℃, add 0.001~5 parts of catalyst and 0.001~1 parts of polymerization inhibitor to solution A by molar, and then slowly add 100~400 parts of glycidyl methacrylate. React for 3~6 hours to obtain solution B.

[0008] (3) The organic solvent was removed by vacuum concentration to obtain bismaleimide-polyetheramine photocurable resin.

[0009] Preferably, the bismaleimide-polyetheramine photocurable resin has the following structural formula:

[0010]

[0011] Where n = 3, 6, 33 or 66, and R is any of the following groups:

[0012] .

[0013] Preferably, the bismaleimide is N,N'-1,3-phenylenebismaleimide, 4,4'-diphenylmethanebismaleimide, or a combination thereof.

[0014] Preferably, the polyetheramine is at least one of D230 (n=3), D400 (n=6), D2000 (n=33), and D4000 (n=66).

[0015] Preferably, the organic solvent is acetone, dichloroethane, tetrahydrofuran, chloroform, or acetonitrile.

[0016] Preferably, the catalyst in step (1) is glacial acetic acid or zinc chloride.

[0017] Preferably, the catalyst in step (2) is at least one of tetrabutylammonium bromide, tetrabutylammonium chloride, tetraethylammonium bromide, tetrabutylammonium hydrogen sulfate, benzyltriethylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride.

[0018] Preferably, the polymerization inhibitor in step (2) is at least one of hydroquinone, benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone.

[0019] Compared with existing technologies, the beneficial effects of this invention are as follows: the bismaleimide-polyetheramine photocurable resin provided by this invention has a wide range of raw material sources, is inexpensive, and has a simple synthesis process, making it suitable for large-scale production and application. Introducing polyetheramine and glycidyl methacrylate into the bismaleimide resin significantly improves the resin's thermal properties and photosensitivity. Simultaneously, expanding the carbon-oxygen bond as the main chain structure gives the resin high thermal stability and weather resistance. The high stability of the carbon-oxygen bond allows the bismaleimide-based resin to maintain stable performance under various harsh environments. In terms of processing, curing can be achieved through ultraviolet light irradiation, with low dimensional shrinkage, effectively solving its poor moldability. The resulting resin has excellent heat resistance, mechanical properties, and photocurability, and can be widely used in photocurable materials, electronic packaging materials, and other fields. Attached Figure Description

[0020] Figure 1 This is the reaction involved in the present invention.

[0021] Figure 2 This is the infrared spectrum of the bismaleimide-polyetheramine photocurable resin prepared in Example 1 of this invention.

[0022] Figure 3 The 1H NMR spectrum of the bismaleimide-polyetheramine photocurable resin prepared in Example 1 of this invention (… 1 H-NMR). Detailed Implementation

[0023] Example 1

[0024] A method for preparing a bismaleimide-polyetheramine photocurable resin includes the following steps:

[0025] (1) Under nitrogen protection at a temperature of 70 °C, 0.05 mol of 4,4'-diphenylmethane bismaleimide (BDM) was dissolved in acetone as a solvent, and then 0.1 mol of polyetheramine D400 was slowly added dropwise, followed by the addition of 0.002 mol of glacial acetic acid. The intermediate (BDM-D400) was obtained after reacting for 2 hours.

[0026] (2) Add 0.002 mol tetraethylammonium bromide and 0.0002 mol hydroquinone, then slowly add 0.2 mol glycidyl methacrylate (GMA) and react at 70 °C for 3 hours.

[0027] (3) Acetone was removed by vacuum concentration to obtain bismaleimide-polyetheramine photocurable resin BDM-D400-GMA (BDG), with the following structural formula.

[0028]

[0029] See appendix Figure 2 This is the Fourier Transform Infrared (FTIR) spectrum of the bismaleimide-polyetheramine photocurable resin prepared in Example 1. In the D400 curve, 3409~3280 cm⁻¹ -1 The range represents the absorption peak of the stretching vibration of -NH2, from 3007 to 2820 cm⁻¹. -1 The peak at 1200–1035 cm⁻¹ corresponds to the CH stretching vibration on the polyether backbone. -1 The strong absorption peak in the range corresponds to the COC stretching vibration, a characteristic absorption of D400 as a polyetheramine. In the BDM-D400 curve, the peak is at 1712 cm⁻¹. -1 The peak at 1513 cm⁻¹ corresponds to the C=O stretching vibration of the carbonyl group in the maleimide ring. -1 The peak at 1617 cm⁻¹ represents the C=C stretching vibration of the benzene ring skeleton in the BDM molecule, indicating that BDM was successfully grafted onto D400. In the BDM-D400-GMA curve, the peak at 1617 cm⁻¹ represents the C=C stretching vibration of the benzene ring skeleton in the BDM molecule, indicating successful grafting of BDM with ... -1 The characteristic peak at 1636 cm⁻¹ is attributed to the CO stretching vibration in the ester group (-COO-). -1 The peak at the point represents the C=C stretching vibration, indicating that GMA successfully reacted with BDM-D400, representing the successful synthesis of the photosensitive prepolymer BDM-D400-GMA (BDG).

[0030] See appendix Figure 3 It is the 1H NMR spectrum of the bismaleimide-polyetheramine photocurable resin prepared in Example 1. 1 ¹H-NMR. The peak with a chemical shift δ around 7.3 ppm represents the benzene ring proton in BDM. The peaks with δ of 3.1 ppm and 3.2 ppm correspond to the proton peaks after the reaction of the amino group in D400, while the peak of the -OH generated after the ring-opening reaction of D400 with GMA is at 5.6 ppm, and the peak with δ around 6.1 ppm represents the proton peak at -C=C-. In summary, the appearance of all the key characteristic peaks in the ¹H-NMR spectrum is completely consistent with the theoretical structural expectation of the target product BDG prepolymer. This result further confirms the successful synthesis of the expected product BDG prepolymer.

[0031] The prepared bismaleimide-polyetheramine photocurable resin was uniformly coated onto a glass slide, and then subjected to 365 nm ultraviolet light (100 mW / cm²). 2 The resin was treated by irradiation in a UV curing chamber. The prepared resin was poured into a mold, and after complete UV curing, the surface of the product was smooth and the Shore hardness was 82HD.

[0032] Example 2

[0033] A method for preparing a bismaleimide-polyetheramine photocurable resin includes the following steps:

[0034] (1) Under nitrogen protection at a temperature of 70 °C, 0.1 mol of 4,4'-diphenylmethane bismaleimide (BDM) was dissolved in tetrahydrofuran as a solvent, and then 0.2 mol of D230 was slowly added dropwise, followed by 0.004 mol of glacial acetic acid. The intermediate (BDM-D230) was prepared by reacting for 2 hours.

[0035] (2) Add 0.004 mol tetraethylammonium bromide and 0.0004 mol hydroquinone, then slowly add 0.2 mol glycidyl methacrylate (GMA) and react at 70 °C for 3 hours.

[0036] (3) Tetrahydrofuran was removed by vacuum concentration to obtain bismaleimide-polyetheramine photocurable resin (BDM-D230-GMA).

[0037] The prepared bismaleimide photosensitive resin was uniformly coated onto a glass slide, and then subjected to 365 nm ultraviolet light (100 mW / cm²). 2 The resin was treated by irradiation in a UV curing chamber. The prepared resin was poured into a mold, and after complete UV curing, the surface of the product was smooth and the Shore hardness was 86HD.

[0038] Example 3

[0039] A method for preparing a bismaleimide-polyetheramine photocurable resin includes the following steps:

[0040] (1) Under nitrogen protection at a temperature of 70 °C, 0.05 mol N,N'-1,3-phenylenebismaleimide (BMI) was dissolved in acetone as a solvent, and then 0.1 mol D400 was slowly added dropwise, followed by 0.002 mol glacial acetic acid. The intermediate (BMI-D400) was obtained after reacting for 2 hours.

[0041] (2) Add 0.002 mol tetraethylammonium bromide and 0.0002 mol hydroquinone, then slowly add 0.2 mol glycidyl methacrylate (GMA) and react at 70 °C for 3 hours.

[0042] (3) Acetone was removed by vacuum concentration to obtain modified bismaleimide resin (BMI-D400-GMA).

[0043] The prepared bismaleimide photosensitive resin was uniformly coated onto a glass slide, and then subjected to 365 nm ultraviolet light (100 mW / cm²). 2The resin was treated by irradiation in a UV curing chamber. The prepared resin was poured into a mold, and after complete UV curing, the surface of the product was smooth and the Shore hardness was 80 HD.

[0044] Example 4

[0045] A method for preparing a bismaleimide-polyetheramine photocurable resin includes the following steps:

[0046] (1) Under nitrogen protection at a temperature of 70 °C, 0.05 mol of 4,4'-diphenylmethane bismaleimide (BDM) was dissolved in tetrahydrofuran as a solvent, and then 0.1 mol of D2000 was slowly added dropwise, followed by 0.002 mol of glacial acetic acid. The intermediate (BDM-D2000) was prepared by reacting for 2 hours.

[0047] (2) Add 0.002 mol tetraethylammonium bromide and 0.0002 mol hydroquinone, then slowly add 0.2 mol glycidyl methacrylate (GMA) and react at 70 °C for 3 hours.

[0048] (3) Tetrahydrofuran was removed by vacuum concentration to obtain modified bismaleimide resin (BDM-D2000-GMA).

[0049] The prepared bismaleimide photosensitive resin was uniformly coated onto a glass slide, and then subjected to 365 nm ultraviolet light (100 mW / cm²). 2 The resin was treated by irradiation in a UV curing chamber. The prepared resin was poured into a mold, and after complete UV curing, the surface of the product was smooth and the Shore hardness was 75 HD.

Claims

1. A method for preparing a bismaleimide-polyetheramine photocured resin, characterized by, It includes the following steps: (1) Under nitrogen protection at a temperature of 50~100 ℃, 100 parts of bismaleimide were added to an organic solvent by molar, then 100~200 parts of polyetheramine were added dropwise, and then 0.001~5 parts of catalyst were added. The reaction was carried out for 1~5 hours to obtain solution A. (2) Under nitrogen protection at a temperature of 50~100 ℃, add 0.001~5 parts of catalyst and 0.001~1 parts of polymerization inhibitor to solution A by molar, then add 100~400 parts of glycidyl methacrylate dropwise, react for 3~6 hours to obtain solution B; (3) The organic solvent was removed by vacuum concentration to obtain bismaleimide-polyetheramine photocurable resin.

2. The method for preparing a bismaleimide-polyetheramine photocurable resin according to claim 1, characterized in that, The structural formula of the bismaleimide-polyetheramine photocurable resin is as follows: ； Where n = 3, 6, 33 or 66, and R is any of the following groups: 。 3. The method for preparing a bismaleimide-polyetheramine photocurable resin according to claim 1, characterized in that, The bismaleimide is N,N'-1,3-phenylenebismaleimide, 4,4'-diphenylmethanebismaleimide, or a combination thereof.

4. The method for preparing a bismaleimide-polyetheramine photocurable resin according to claim 1, characterized in that, The polyetheramine is at least one of D230, D400, D2000, and D4000.

5. The method for preparing a bismaleimide-polyetheramine photocurable resin according to claim 1, characterized in that, The organic solvent is acetone, dichloroethane, tetrahydrofuran, chloroform, or acetonitrile.

6. The method for preparing a bismaleimide-polyetheramine photocurable resin according to claim 1, characterized in that, The catalyst mentioned in step (1) is glacial acetic acid or zinc chloride.

7. The method for preparing a bismaleimide-polyetheramine photocurable resin according to claim 1, characterized in that, The catalyst in step (2) is at least one of tetrabutylammonium bromide, tetrabutylammonium chloride, tetraethylammonium bromide, tetrabutylammonium hydrogen sulfate, benzyltriethylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride.

8. The method for preparing a bismaleimide-polyetheramine photocurable resin according to claim 1, characterized in that, The polymerization inhibitor mentioned in step (2) is at least one of hydroquinone, benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone.

9. The bismaleimide-polyetheramine photocurable resin obtained by the preparation method according to any one of claims 1 to 8.

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