Hyperbranched polyimide as well as preparation method and application thereof
By synthesizing hyperbranched polyimide films without solvent, the problems of environmental pollution and poor photosensitivity in the traditional polyimide preparation process are solved, providing green and environmentally friendly photosensitive materials for use in aerospace and information storage fields.
Patent Information
- Application Number
- CN202510689689.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-27
- Publication Date
- 2025-10-10
AI Technical Summary
Existing polyimide materials rely on high-boiling-point polar solvents during the preparation process, causing environmental pollution and poor photosensitivity, limiting their application in microelectronic devices.
Hyperbranched polyimide was prepared by the reaction of dianhydride compound and hexamethylene diisocyanate isocyanurate trimer using a solvent-free synthesis method. Vanillin was added into the reaction for modification to prepare photosensitive hyperbranched polyimide film.
The green and environmentally friendly polyimide film preparation has been achieved, which has the function of photosensitive color change and is suitable for aerospace, optical information storage and information encryption fields.
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Figure CN120757787A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of polymer materials, and in particular to a hyperbranched polyimide and a preparation method and application thereof. Background Art
[0002] With the rapid development of polymer materials, polyimide (PI) materials are widely used in key fields such as aerospace and microelectronics industries due to their excellent high-temperature resistance, dielectric properties, chemical stability and excellent radiation resistance. However, since commonly used polyimides do not have photosensitivity, other photosensitive materials must be used when they are used as film patterns in microelectronic devices, making the entire photolithography process extremely complex and inefficient. Photosensitive polyimide (PSPI) is a polymer material containing imide rings and photosensitive groups on the main chain. It has both photosensitivity and heat resistance and has become a key material for interlayer insulation materials, α-ray shielding layers, passivation coatings, and chip planarization processes in semiconductor manufacturing.
[0003] Although previously reported PIs exhibit excellent thermal stability and mechanical properties, their preparation relies on highly polar solvents with high boiling points, high curing temperatures, poor photosensitivity, and large shrinkage, limiting their further application. The development of hyperbranched polyimides (HBPIs) and photosensitive polyimides (PSPIs) has alleviated these issues to some extent, but existing synthesis methods often rely on high-boiling polar solvents, which imposes an environmental burden. Therefore, the development of solvent-free photosensitive hyperbranched polyimides (VHPIs) has become an important research direction. This solvent-free synthesis technology not only provides a new approach for preparing environmentally friendly, high-performance PI materials, but also offers new ideas for achieving harmonious coexistence between the environment, society, and the economy. Therefore, there is an urgent need to develop photochromic HBPI materials that not only have mechanical properties comparable to those of traditional high-performance PIs but also can exhibit high performance under specific conditions. This will promote the development of PI materials in a greener and more sustainable direction, with broad application prospects in aerospace, optical information storage, information encryption and decryption, and other fields. Summary of the Invention
[0004] The first technical problem to be solved by the present invention is to provide a photosensitive hyperbranched polyimide.
[0005] In order to solve the above technical problems, the hyperbranched polyimide provided by the present invention has the following structural formula:
[0006]
[0007] Among them, the structural formula of O is The structural formula of AB2AO is The structural formula of A-NCO is The structural formula of X is In the structural formula, e is a natural number of 1-2, m is a natural number of 2-4, and y is a natural number of 4-8.
[0008] The hyperbranched polyimide provided by the present invention may also be a compound having the following structural formula:
[0009]
[0010] Among them, the structural formula of O is The structural formula of AB2AO is The structural formula of A-NCO is: The structural formula of AC is The structural formula of X is
[0011] At least one of .
[0012] In the structural formula, e is a natural number from 1 to 2, g is a natural number from 0 to 1, f is a natural number from 0 to 6e, and g and f cannot be 0 at the same time; m is a natural number from 2 to 4, p is a natural number from 0 to 2, n is a natural number from 0 to 6m, and p and n cannot be 0 at the same time; y is a natural number from 5 to 8, w is a natural number from 0 to 3, and z is a natural number from 0 to 6y, and w and z cannot be 0 at the same time.
[0013] According to the above scheme, f is a natural number from 6 to 12, n is a natural number from 6 to 24, and z is a natural number from 6 to 48.
[0014] The second technical problem to be solved by the present invention is to provide a method for preparing the hyperbranched polyimide.
[0015] To solve the above technical problems, the technical solution provided by the present invention includes the following steps:
[0016] (1) A dianhydride compound and a hexamethylene diisocyanate isocyanurate trimer (HDI-trimer) were mixed uniformly in a molar ratio of 1:(1.02-1.11), stirred under an inert atmosphere, heated to 100-120°C, and then a catalyst was added. The temperature was further raised to 150-170°C and reacted for 8-12 hours to prepare a hyperbranched polyimide (HBPI).
[0017] (2) Vanillin was added to a portion of the HBPI prepared in step (1) and mixed evenly, and the mixture was cooled to 70-90° C., and stirred for 7-12 hours under the action of a catalyst DBTDL to prepare vanillin-based hyperbranched polyimide (VHPI).
[0018] According to the above scheme, the dianhydride compound in the reaction of step (1) is at least one of pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic dianhydride.
[0019] According to the above scheme, the catalyst required for the reaction of step (1) is prepared by dissolving N,N-dimethylcyclohexylamine and di-n-butylamine in triethyl phosphate in a molar ratio of 2:1.
[0020] According to the above scheme, in step (2), the HBPI and vanillin are added in a ratio of 1:1-48, and the DBTDL is added in an amount of 1-15%.
[0021] The present invention also provides the use of the hyperbranched polyimide as a photosensitive material. When used as a photosensitive material, preferably in the form of a film, the HBPI sample from step (1) and the VHPI sample from step (2) can be introduced into a mold and cooled to room temperature to prepare a hyperbranched polyimide film.
[0022] The beneficial effects of the present invention are as follows: the photosensitive hyperbranched polyimide prepared based on a dianhydride compound and a hexamethylene diisocyanate isocyanurate trimer (HDI-trimer) provided by the present invention does not contain an organic solvent, has a simple preparation method, mild reaction conditions, does not use any organic solvent during the preparation process, and does not generate toxic or hazardous waste. The present invention is green, environmentally friendly, economical and practical, and is conducive to industrial production. The prepared HBPI film has a photosensitive color-changing function and can maintain the color for a relatively short time; the VHPI film prepared by further modification has a photosensitive color-changing function and can maintain the color for a relatively long time, and has broad application prospects in aerospace, optical information storage, information encryption and decryption and other fields. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 This is the ultraviolet color-changing pattern of the hyperbranched polyimide HBPI prepared in Example 1.
[0024] Figure 2 This is the ultraviolet color-changing cycling pattern of the vanillin-based hyperbranched polyimide (VHPI-1) prepared in Example 6.
[0025] Figure 3 This is the ultraviolet color-changing cycling pattern of the vanillin-based hyperbranched polyimide (VHPI-2) prepared in Example 7.
[0026] Figure 4 This is the ultraviolet color-changing cycle pattern of the vanillin-based hyperbranched polyimide (VHPI-3) prepared in Example 8.
[0027] Figure 5These are the ultraviolet color-changing patterns of vanillin-based hyperbranched polyimides (VHPI-1, VHPI-2, VHPI-3) prepared in Examples 6, 7, and 8. DETAILED DESCRIPTION
[0028] The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are all commercially available products.
[0029] Example 1
[0030] A photosensitive hyperbranched polyimide, the preparation method of which comprises the following specific steps:
[0031] Pyromellitic dianhydride (2.18 g, 10 mmol) and hexamethylene diisocyanate trimer (5.14 g, 10.2 mmol) were mixed in a molar ratio of 1:1.02. The reaction conditions were as follows: the mixture was heated to 100°C with stirring under a nitrogen atmosphere, and then N,N-dimethylcyclohexylamine (0.02 g, 0.15 mmol), di-n-butylamine (0.04 g, 0.31 mmol), and triethyl phosphate (0.08 g, 0.44 mmol) were added. The mixture was heated to 150°C and stirred for 12 hours to prepare a hyperbranched polyimide (HBPI) having the structure of Formula 3, wherein y is 8 in this embodiment and X is X1 in this embodiment.
[0032] Pour the HBPI sample into the mold and cool it to room temperature to obtain a hyperbranched polyimide HBPI film. Cut the paper into a circular hollow pattern shape, cover the pattern on the hyperbranched polyimide HBPI film, and irradiate it with a 365nm ultraviolet lamp for 10s. Figure 1 It can be seen that after irradiation with ultraviolet light, the color of the film pattern turns blue-green; within 3 seconds after the ultraviolet light is removed, the color of the blue-green HBPI film gradually becomes lighter and disappears quickly.
[0033] Example 2
[0034] A photosensitive hyperbranched polyimide, the preparation method of which comprises the following specific steps:
[0035] 3,3',4,4'-Biphenyltetracarboxylic dianhydride (2.94 g, 10 mmol) and hexamethylene diisocyanate trimer (5.28 g, 10.47 mmol) were mixed at a molar ratio of 1:1.047. The reaction conditions were as follows: the mixture was heated to 110°C with stirring under a nitrogen atmosphere, and then N,N-dimethylcyclohexylamine (0.02 g, 0.15 mmol), di-n-butylamine (0.04 g, 0.31 mmol) (the structure of Formula 2), and triethyl phosphate (0.08 g, 0.44 mmol) were added. The mixture was heated to 155°C and stirred for 12 hours to prepare a hyperbranched polyimide (HBPI-1), wherein m is 4 in this embodiment and X is X2 in this embodiment.
[0036] Example 3
[0037] A photosensitive hyperbranched polyimide, the preparation method of which comprises the following specific steps:
[0038] 1,4,5,8-naphthalenetetracarboxylic anhydride (2.68 g, 10 mmol) and hexamethylene diisocyanate trimer (5.544 g, 11 mmol) were mixed in a molar ratio of 1:1.1. The reaction conditions were as follows: the mixture was heated to 115°C with stirring under a nitrogen atmosphere, and then N,N-dimethylcyclohexylamine (0.02 g, 0.15 mmol), di-n-butylamine (0.04 g, 0.31 mmol), and triethyl phosphate (0.08 g, 0.44 mmol) were added. The mixture was heated to 160°C and stirred for 12 hours to prepare a hyperbranched polyimide (HBPI-2) having the structure of Formula 1, wherein e is 2 in this embodiment, and X is X3 in this embodiment.
[0039] Example 4
[0040] A photosensitive hyperbranched polyimide, the preparation method of which comprises the following specific steps:
[0041] 1,2,4,5-cyclohexanetetracarboxylic dianhydride (2.24 g, 10 mmol) and hexamethylene diisocyanate trimer (5.191 g, 10.3 mmol) were mixed in a molar ratio of 1:1.03. The reaction conditions were as follows: the mixture was heated to 118°C under a nitrogen atmosphere with stirring, and then N,N-dimethylcyclohexylamine (0.02 g, 0.15 mmol), di-n-butylamine (0.04 g, 0.31 mmol), and triethyl phosphate (0.08 g, 0.44 mmol) were added. The mixture was heated to 165°C and stirred for 12 hours to prepare a hyperbranched polyimide (HBPI-3) having the structure of Formula 3, wherein y is 4 in this embodiment and X is X4 in this embodiment.
[0042] Example 5
[0043] A photosensitive hyperbranched polyimide, the preparation method of which comprises the following specific steps:
[0044] 2,3,6,7-Naphthalenetetracarboxylic dianhydride (2.68 g, 10 mmol) and hexamethylene diisocyanate trimer (5.226 g, 10.37 mmol) were mixed at a molar ratio of 1:1.037. The reaction conditions were as follows: the mixture was heated to 120°C with stirring under a nitrogen atmosphere, and then N,N-dimethylcyclohexylamine (0.02 g, 0.15 mmol), di-n-butylamine (0.04 g, 0.31 mmol), and triethyl phosphate (0.08 g, 0.44 mmol) were added. The mixture was heated to 170°C and stirred for 12 hours to prepare a hyperbranched polyimide (HBPI-4) having the structure of Formula 3, wherein y is 2 in this embodiment and X is X5 in this embodiment.
[0045] Example 6
[0046] A photosensitive hyperbranched polyimide, the preparation method of which comprises the following specific steps:
[0047] After preparing the hyperbranched polyimide according to Example 1, 1 mmol of the product was cooled to 70° C., and vanillin (3.648 g, 24 mmol) and DBTDL (0.05 g, 0.08 mmol) were added and stirred for 10 hours to obtain a hyperbranched polyimide (VHPI-1) with an aldehyde terminal group as shown in Formula 6, wherein z is 24 in this embodiment and w is 0.
[0048] The VHPI-1 sample was poured into the mold and cooled to room temperature to obtain the VHPI-1 film. Figure 2 As can be seen, when paper is cut into hollow "S," "C," "M," and "U" patterns, the "S" pattern is overlaid on a hyperbranched polyimide VHPI-1 film, and irradiated with a 365nm UV lamp for 20 seconds, the film pattern changes color to green. After 30 minutes of UV lamp removal, significant fading occurs. After 60 minutes, the color fades almost completely, but a light yellow mark remains. After 90 minutes, the pattern disappears completely, leaving no trace. By irradiating again and overlaying the "C," "M," and "U" patterns on a hyperbranched polyimide VHPI-2 film, the color-changing "C," "M," and "U" film patterns can be re-obtained, and can be reused multiple times.
[0049] Example 7
[0050] A photosensitive hyperbranched polyimide, the preparation method of which comprises the following specific steps:
[0051] After preparing the hyperbranched polyimide HBPI according to Example 1, 2 mmol of the product was cooled to 70° C., vanillin (3.04 g, 20 mmol) and DBTDL (0.1 g, 0.16 mmol) were added and stirred for 9 hours to obtain a hyperbranched polyimide (VHPI-2) having an aldehyde terminal group as shown in Formula 6, wherein z is 10 and w is 0 in this embodiment.
[0052] The VHPI-2 sample was poured into a mold and cooled to room temperature to obtain a hyperbranched polyimide VHPI-2 film. Figure 3 As can be seen, when paper is cut into hollow "S," "C," "M," and "U" patterns, the "S" pattern is overlaid on a hyperbranched polyimide VHPI-2 film, and irradiated with a 365nm UV lamp for 30 seconds, the film pattern changes color to green. One hour after the UV lamp is removed, significant fading occurs. After 90 minutes, the color fades almost completely, but a light yellow mark remains. After 3 hours, the pattern disappears completely, leaving no trace. Repeated irradiation, followed by overlaying the "C," "M," and "U" patterns on a hyperbranched polyimide VHPI-1 film, regenerates the color-shifting "C," "M," and "U" film patterns, which can be reused multiple times.
[0053] Example 8
[0054] A photosensitive hyperbranched polyimide, the preparation method of which comprises the following specific steps:
[0055] After preparing the hyperbranched polyimide according to Example 1, 1 mmol of the product was cooled to 70° C., and vanillin (7.296 g, 48 mmol) and DBTDL (0.05 g, 0.08 mmol) were added and stirred for 12 hours to obtain a hyperbranched polyimide (VHPI-3) with an aldehyde terminal group as shown in Formula 6, wherein z is 48 in this embodiment and w is 0.
[0056] The VHPI-3 sample was poured into the mold and cooled to room temperature to obtain the VHPI-3 film. Figure 4 As can be seen, when paper is cut into hollow "S," "C," "M," and "U" patterns, the "S" pattern is overlaid on a hyperbranched polyimide (VHPI-3) film, and irradiated with a 365nm UV lamp for 60 seconds, the film pattern changes color to green. One hour after the UV lamp is removed, the color begins to fade, becoming more noticeable after three hours. After four hours, it fades to a very light yellow, and after six hours, the pattern disappears completely without leaving any trace. By irradiating the film again and overlaying the "C," "M," and "U" patterns on the hyperbranched polyimide (VHPI-3) film in that order, the color-changing "C," "M," and "U" film patterns can be re-obtained, allowing for repeated use.
[0057] from Figure 5 As can be seen, the paper was cut into a "five-pointed star" hollow pattern shape, the "five-pointed star" pattern was respectively covered on the hyperbranched polyimide VHPI-1, VHPI-2, VHPI-3 film, and irradiated by a 365 nm ultraviolet lamp for 30 s, the film pattern color changed to green; after removing the ultraviolet lamp, the color began to fade until completely faded. Re-irradiation can re-obtain the film discoloration pattern, which can be repeatedly used for many times. Among them, VHPI-2 requires the shortest time to completely fade, while VHPI-3 requires the longest time to completely fade, which is consistent with the experimental results of the "S", "C", "M", "U" hollow pattern shapes in the previous.
[0058] Although the present application has been described in detail with general description and specific embodiments, some modifications or improvements can be made on the basis of the present application, which is obvious to those skilled in the art. Therefore, these modifications or improvements made on the basis of not deviating from the spirit of the present application, all belong to the scope of the present application claimed.
Claims
1. A hyperbranched polyimide, characterized in that: The hyperbranched polyimide has the following structural formula: Among them, the structural formula of O is The structural formula of AB2AO is The structural formula of A-NCO is The structural formula of X is At least one of; wherein the structural formula, e is a natural number of 1-2, m is a natural number of 2-4, and y is a natural number of 4-8.
2. A hyperbranched polyimide, characterized in that The hyperbranched polyimide has the following structural formula: Among them, the structural formula of O is The structural formula of AB2AO is The structural formula of A-NCO is The structural formula of AC is The structural formula of X is At least one of; In the structural formula, e is a natural number from 1 to 2, g is a natural number from 0 to 1, f is a natural number from 0 to 6e, and g and f cannot be 0 at the same time; m is a natural number from 2 to 4, p is a natural number from 0 to 2, n is a natural number from 0 to 6m, and p and n cannot be 0 at the same time; y is a natural number from 5 to 8, w is a natural number from 0 to 3, and z is a natural number from 0 to 6y, and w and z cannot be 0 at the same time.
3. The hyperbranched polyimide according to claim 2, wherein f is a natural number from 6 to 12, n is a natural number from 6 to 24, and z is a natural number from 6 to 48.
4. A method for preparing a hyperbranched polyimide, characterized in that: The method is: The dianhydride compound and hexamethylene diisocyanate isocyanurate trimer were mixed uniformly in a molar ratio of 1: (1.02-1.11), stirred under an inert atmosphere, heated to 100-120°C, and then a hyperbranched catalyst was added. The temperature was further raised to 150-170°C and reacted for 8-12 hours to prepare a hyperbranched polyimide HBPI.
5. The method for preparing a hyperbranched polyimide according to claim 4, wherein The method further comprises the following steps: Vanillin is added to the prepared hyperbranched polyimide HBPI and mixed evenly. The mixture is cooled to 70-90° C. and stirred for reaction for 7-12 hours under the action of catalyst DBTDL to prepare vanillin-based hyperbranched polyimide VHPI.
6. The method for preparing a hyperbranched polyimide according to claim 4 or 5, wherein The dianhydride compound is at least one of pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic dianhydride.
7. The method for preparing a hyperbranched polyimide according to claim 4 or 5, wherein: The hyperbranched catalyst is prepared by dissolving N,N-dimethylcyclohexylamine and di-n-butylamine in triethyl phosphate in a molar ratio of 2:
1.
8. The method for preparing a hyperbranched polyimide according to claim 5, wherein The HBPI and vanillin are added in a ratio of 1:1-48, and the DBTDL is added in an amount of 1-15%.
9. Use of the hyperbranched polyimide according to claim 1 or 2 as a photosensitive material.
10. Use of the hyperbranched polyimide according to claim 9 as a photosensitive material, characterized in that: The hyperbranched polyimide is in a thin film state when used as a photosensitive material.