A silicone macromolecular azido coupling agent and a method for preparing the same

Abstract

The application discloses a kind of organic silicon macromolecular azide coupling agent and preparation method thereof.The organic silicon macromolecular azide coupling agent includes three main chain structures: linear single chain structure, ladder double chain structure and three chain structure.The organic silicon azide coupling agent of the application is easy to break and recombine under the condition of ultraviolet light irradiation, thereby realizing the crosslinking of material.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of organic silicon macromolecular azide coupling agent and its preparation method, more particularly to a kind of macromolecular photocoupling agent containing organic silicon structure and azide functional group, specifically to linear single chain, ladder double chain and three chain structure organic silicon macromolecular azide coupling agent and its preparation method.The technology is mainly applied to photosensitive material, photoresist, UV-CTP plate and OLED display, belongs to the field of organic silicon functional materials. BACKGROUND

[0002] Small molecule photocrosslinker is a kind of compound which can generate high active intermediate under the irradiation of specific wavelength of light, and form covalent bond with its acceptor active site.These crosslinkers are widely used in photoresist, photosensitive coating and biological research due to their unique photosensitive properties.According to the different active intermediates generated under light irradiation, small molecule photocrosslinker can be divided into the following four categories: the first category is nitrenes, which mainly releases nitrogen through azide group on the aromatic ring under light irradiation to form high active nitrene intermediate.Nitrene intermediate can be singlet or triplet state through intersystem crossing, and its singlet state can insert into C-H bond or X-H bond (X=N, O, S) to form stable covalent bond.This mechanism gives nitrene photocrosslinker high crosslinking performance.The second category is carbenes, including diazocompounds and bis-aziridines.Diazocompounds release nitrogen to form carbene intermediate under UV irradiation, and then react with adjacent C-H bond to form new covalent bond.Bis-aziridines also generate carbene intermediate through similar process and react with the matrix to complete crosslinking.The third category is carbocations, represented by aromatic diazonium salt.These compounds generate aromatic cationic intermediate under UV irradiation and react with adjacent C-H bond or other heteroatom-hydrogen bond to form stable crosslinking structure.The fourth category is radicals, which generate radicals under light irradiation and initiate crosslinking reaction between molecules to form network structure.

[0003] Among the above types, azide small molecule photocrosslinker occupies an important position in many applications due to its unique advantages.The main advantages include: (1) chemical stability: can resist ordinary chemical environment without decomposition. (2) light stability: good stability in natural light and darkness, not easy to decompose spontaneously. (3) rapid photolysis: can rapidly photolyze under UV irradiation to generate high active nitrene intermediate. (4) high reactivity: the generated intermediate can react with nucleophilic functional groups (such as X-H bond, X=N, O, S) and also can insert into C-H bond to form covalent bond.

[0004] Despite the advantages of azide-based small molecule photocrosslinkers, they also have some disadvantages that cannot be ignored. For example, in some cases, non-specific crosslinking of this type of crosslinker may occur. If the active site of the matrix lacks nucleophilic functional groups, the active intermediate may migrate away from the target area, leading to non-ideal crosslinking. In addition, small molecule azide compounds have small molecular weights, which leads to uneven distribution in the material, which may affect the final crosslinking effect and material performance consistency.

[0005] Organosilicon materials have become an important part of modern polymer materials due to their unique properties. Their thermal stability, chemical inertness, and excellent mechanical properties make them irreplaceable in many fields. The high bond energy of the silicon-oxygen bond gives organosilicon materials excellent thermal stability and weather resistance; its flexible molecular backbone also makes the material have excellent processing performance and elasticity. More importantly, organosilicon materials can be designed through various chemical routes, such as linear single-chain, ladder double-chain, and triple-chain structures, to meet the needs of functionalization and structuring in different fields. SUMMARY

[0006] In order to overcome these disadvantages, we tried to introduce azide functional groups into the organosilicon macromolecular structure. Through this design, the storage stability and crosslinking uniformity of the azide-based photocrosslinker can be improved while retaining its photosensitive activity.

[0007] The present application introduces azide functional groups into organosilicon macromolecules, which not only inherits the high efficiency of azide-based photocrosslinking, but also significantly improves the stability and processing performance of the material. This innovative design uses organosilicon macromolecules as carriers to evenly distribute azide groups on the main chain, avoiding the problem of uncontrollable crosslinking density in traditional small molecule azide coupling agents, while significantly reducing toxicity and explosion risk.

[0008] The present application aims to provide an organosilicon macromolecular azide coupling agent with excellent performance.

[0009] The organosilicon macromolecular azide coupling agent provided by the present application comprises three main chain structures:

[0010] (1) Linear single-chain structure, the structural formula is shown as formula (1); has good flexibility and easy processability, suitable for low crosslinking density materials;

[0011] (2) Ladder double-chain structure, the structural formula is shown as formula (2); improves the spatial stability and intermolecular forces of the material, suitable for high strength applications;

[0012] (3) Triple-chain structure, the structural formula is shown as formula (3); while increasing the crosslinking density, it gives the material higher thermal stability and mechanical strength;

[0013]

[0014] In equations (1), (2), and (3), R1, R2, R3, and R4 independently represent hydrogen atoms, C1-C atoms, and C1-C atoms, respectively. 10 Straight-chain or branched alkyl groups (specifically C1-C6 straight-chain or branched alkyl groups, such as methyl or ethyl), mercapto, substituted or unsubstituted aromatic groups (such as phenyl), C2-C 10 Alkenyl (specifically C2-C6 alkenyl, such as vinyl and propenyl), ( Indicates C1-C6 straight-chain or branched alkylene or n is an integer from 1 to 3, specifically one of the following (1), and at least one of R1, R2, R3, and R4 is

[0015] x and y represent any values ​​from 1 to 10;

[0016] R5 represents the end-capping group, which can be any one of the following end-capping agents: trimethylchlorosilane, dimethylvinylchlorosilane, and dimethylphenylchlorosilane, obtained by removing chlorine.

[0017] This invention also provides a method for preparing the above-mentioned organosilicon macromolecular azide coupling agent, wherein R1 is... The preparation method of the compound shown in formula (1) is as follows: The compound shown in formula (4) is dissolved in an acid solution, cooled to the reaction temperature, and sodium nitrite aqueous solution and sodium azide aqueous solution are added sequentially. After the reaction is completed, the mixture is filtered, washed with water, and recrystallized with acetone to obtain the compound shown in formula (1).

[0018]

[0019] In equation (4), the definitions of R2, R3, R4, R5, x, and y are the same as those in equation (1);

[0020] In the above method, the acid is selected from at least one of hydrochloric acid, sulfuric acid, and nitric acid;

[0021] The molar ratio of the compound shown in formula (4) to sodium nitrite and sodium azide can be 1:1-2:1-2 respectively;

[0022] The reaction temperature is 0-10℃, and the preferred reaction temperature is 0-4℃;

[0023] The reaction time can be 0.2-3 hours.

[0024] The compound shown in formula (4) above is prepared by a method comprising the following steps:

[0025] dissolving a compound shown in formula (5) and a compound shown in formula (6) in an organic solvent, adding a palladium catalyst, a ligand, a base, and performing a Heck reaction to obtain a compound shown in formula (4);

[0026]

[0027] In formula (5), definitions of R2, R3, R4, R5, x and y are the same as those of R2, R3, R4, R5, x and y in formula (1).

[0028] In the above method, the palladium catalyst is Pd(OAc)2 or Pd(PPh3)4.

[0029] The ligand can be specifically tris(o-tolyl)phosphine.

[0030] The base is at least one selected from potassium carbonate, sodium carbonate, sodium hydroxide, sodium carbonate-sodium hydroxide, potassium bicarbonate and triethylamine.

[0031] The temperature of the Heck reaction can be 60-120°C, and the time can be 0.2-5h.

[0032] The compound shown in formula (5) is prepared by a method comprising the following steps: dissolving a compound shown in formula (7) and a compound shown in formula (8) in a hydrolysis condensation reaction, and adding a blocking agent R5-Cl to obtain the compound shown in formula (5).

[0033]

[0034] In formula (7), definitions of R2 and x are the same as those of R2 and x in formula (1).

[0035] In formula (8), definitions of R3, R4 and y are the same as those of R3, R4 and y in formula (1).

[0036] In R5-Cl, the definition of R5 is the same as that of R5 in formula (1).

[0037] The compound shown in formula (7) can be prepared by hydrolysis condensation of a compound shown in formula (9), and the compound shown in formula (8) can be prepared by hydrolysis condensation of a compound shown in formula (10).

[0038]

[0039] R1 is When R1 is, a preparation method of the compound shown in formula (2) is as follows: dissolving a compound shown in formula (11) in an acid solution, cooling to a reaction temperature, sequentially adding an aqueous sodium nitrite solution and an aqueous sodium azide solution, after the reaction is completed, performing water washing by suction filtration, and performing acetone recrystallization to obtain the compound shown in formula (2),

[0040]

[0041] R2, R3, R4, R5, x, y in formula (11) are defined as R2, R3, R4, R5, x, y in formula (2);

[0042] In the method, the acid is at least one selected from hydrochloric acid, sulfuric acid and nitric acid;

[0043] The molar ratio of the compound shown in formula (11) to sodium nitrite and sodium azide can be 1:1-2:1-2, respectively;

[0044] The reaction temperature is 0-10℃, and the preferred reaction temperature is 0-4℃;

[0045] The reaction time can be 0.2-3h.

[0046] The compound shown in formula (11) is prepared by a method comprising the following steps:

[0047] The compound shown in formula (12) and the compound shown in formula (6) are dissolved in an organic solvent, a palladium catalyst, a ligand, a base are added, and a Heck reaction is carried out to obtain the compound shown in formula (11);

[0048]

[0049] In formula (12), R2, R3, R4, R5, x, y are defined as R2, R3, R4, R5, x, y in formula (2)

[0050] In the method, the palladium catalyst is Pd(OAc)2 or Pd(PPh3)4;

[0051] The ligand can be specifically tris(o-tolyl)phosphine;

[0052] The base is at least one selected from potassium carbonate, sodium carbonate, sodium hydroxide, sodium carbonate-sodium hydroxide, potassium bicarbonate, and triethylamine;

[0053] The temperature of the Heck reaction can be 60-120℃, and the time can be 0.2-5h.

[0054] The compound shown in formula (12) is prepared by a method comprising the following steps: dissolving the compounds shown in formula (13) and formula (14), hydrolysis condensation reaction, and adding a capping agent R5-Cl to obtain the compound shown in formula (12);

[0055]

[0056] In formula (13), R2, x are defined as R2, x in formula (2);

[0057] In formula (14), R3, R4, and y are defined as in formula (2).

[0058] The compound represented by formula (13) is prepared by dissolving a compound represented by formula (15) and a compound represented by formula (16) and subjecting them to hydrolytic condensation reaction.

[0059]

[0060] In formula (16), R2 is defined as in formula (2).

[0061] The compound represented by formula (14) is prepared by dissolving a compound represented by formula (17) and a compound represented by formula (18) and subjecting them to hydrolytic condensation reaction.

[0062]

[0063] In formula (17), R3 is defined as in formula (2).

[0064] In formula (18), R4 is defined as in formula (2).

[0065] R1 is When R1 is -CH2OH, the compound represented by formula (3) is prepared by dissolving a compound represented by formula (19) in an acid solution, cooling to a reaction temperature, sequentially adding an aqueous sodium nitrite solution and an aqueous sodium azide solution, and after the reaction is completed, filtering and washing with water, and recrystallizing from acetone to obtain the compound represented by formula (3).

[0066]

[0067] In formula (19), R2, R3, R4, R5, x, and y are defined as in formula (3).

[0068] In the above method, the acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, and nitric acid.

[0069] The molar ratio of the compound represented by formula (19) to sodium nitrite and sodium azide is 1:1-2:1-2, respectively.

[0070] The reaction temperature is 0-10°C, and preferably 0-4°C.

[0071] The reaction time is 0.2-3h.

[0072] The compound represented by formula (19) is prepared by a method comprising the following steps:

[0073] dissolving the compound shown in formula (20) and the compound shown in formula (6) in an organic solvent, adding a palladium catalyst, a ligand, a base, and performing a Heck reaction to obtain the compound shown in formula (19);

[0074]

[0075] In formula (20), the definitions of R2, R3, R4, R5, x, and y are the same as those of R2, R3, R4, R5, x, and y in formula (3);

[0076] In the above method, the palladium catalyst is Pd(OAc)2 or Pd(PPh3)4;

[0077] The ligand can be specifically tris(o-tolyl)phosphine;

[0078] The base is selected from at least one of potassium carbonate, sodium carbonate, sodium hydroxide, sodium carbonate-sodium hydroxide, potassium bicarbonate, and triethylamine;

[0079] The temperature of the Heck reaction can be 60-120°C, and the time can be 0.2-5h.

[0080] The compound shown in formula (20) is prepared by a method comprising the following steps: dissolving the compound shown in formula (21) and the compound shown in formula (22), hydrolytic condensation reaction, and adding a capping agent R5-Cl to obtain the compound shown in formula (20):

[0081]

[0082] In formula (21), the definitions of R2 and x are the same as those of R2 and x in formula (3);

[0083] In formula (22), the definitions of R3, R4, and y are the same as those of R3, R4, and y in formula (3);

[0084] The definition of R5 in R5-Cl is the same as that of R5 in formula (3)

[0085] The compound shown in formula (21) is prepared by hydrolytic condensation of the compounds shown in formula (15), formula (16), and formula (23);

[0086]

[0087] The compound shown in formula (22) is prepared by hydrolytic condensation of the compounds shown in formula (17), formula (18), and formula (23).

[0088] The above organosilicon macromolecular azide coupling agent is used as a photo-induced crosslinking agent in the preparation of photo-induced crosslinking materials (such as photoresists, liquid crystal displays, and biological imaging).

[0089] The above-mentioned organic silicon macromolecular azide coupling agent is prone to cleavage and recombination reaction under ultraviolet light irradiation, thereby realizing crosslinking of the material.

[0090] The above-mentioned organic silicon macromolecular azide coupling agent needs to be stored in low temperature and away from light.

[0091] The above-mentioned organic silicon macromolecular azide coupling agent can be used in photoresist and other photo-crosslinking materials.

[0092] The present application develops a macromolecular azide coupling agent with excellent performance through molecular design, combining linear single chain, ladder double chain and triple chain of various organic silicon structures. The coupling agent of the present application can be efficiently decomposed under ultraviolet light irradiation and realize crosslinking of the material, and has the following advantages: (1) efficient crosslinking: uniform distribution of azide groups improves the uniformity and density of crosslinking; (2) safe and stable: macromolecular structure significantly improves the storage stability of the material, reduces the toxicity and explosion risk; (3) multifunctional adaptation: structural flexibility makes it suitable for photoresist, liquid crystal display and biological imaging and other fields, showing broad application prospects. BRIEF DESCRIPTION OF DRAWINGS

[0093] Figure 1 The effect diagram after exposure and development in Example 10 of the present application. DETAILED DESCRIPTION

[0094] The present application will be further described in detail below in combination with specific embodiments. The examples provided below are only for illustrating the present application, and are not intended to limit the scope of the present application. The examples provided below can serve as a guide for further improvement by those skilled in the art, and do not constitute any limitation on the present application in any way.

[0095] In the following examples, the experimental methods are conventional methods, and are carried out according to the techniques or conditions described in the literature in the art or according to the product instructions, unless otherwise specified. The materials, reagents and the like used in the following examples can be obtained from commercial channels, unless otherwise specified.

[0096] The present application aims to develop an organic silicon macromolecular azide coupling agent with excellent performance, which is unique in that it contains three main chain structures:

[0097] (1) Linear single chain structure: good flexibility and easy processability, suitable for materials with low crosslinking density;

[0098] (2) Ladder double chain structure: improves the spatial stability and intermolecular forces of the material, suitable for high strength applications;

[0099] (3) Triple-chain structure: While increasing the crosslinking density, it endows the material with higher thermal stability and mechanical strength. This includes, but is not limited to, an organosilicon macromolecular azide coupling agent and its preparation method.

[0100] The organosilicon macromolecular azide coupling agent is mainly composed of compounds represented by the following three structures:

[0101]

[0102] In equations (1), (2), and (3), R1, R2, R3, and R4 independently represent hydrogen atoms, C1-C atoms, and C1-C atoms, respectively. 10 Straight-chain or branched alkyl groups (specifically C1-C6 straight-chain or branched alkyl groups, such as methyl or ethyl), mercapto, substituted or unsubstituted aromatic groups (such as phenyl), C2-C 10 Alkenyl (specifically C2-C6 alkenyl, such as vinyl and propenyl), ( Indicates C1-C6 straight-chain or branched alkylene or n is an integer from 1 to 3, specifically one of the following (1), and at least one of R1, R2, R3, and R4 is

[0103] x and y represent any values ​​from 1 to 10;

[0104] R5 represents the end-capping group, which can be any one of the following end-capping agents: trimethylchlorosilane, dimethylvinylchlorosilane, or dimethylphenylchlorosilane, obtained by removing chlorine from the group.

[0105] In some embodiments, taking x = 3 and y = 3 as examples, the typical structure represented by equation (1) includes:

[0106]

[0107] In some embodiments, taking x = 3 and y = 3 as examples, the typical structure represented by equation (2) includes:

[0108]

[0109] In some embodiments, taking x = 3 and y = 3 as examples, the typical structure represented by equation (3) includes:

[0110]

[0111] Example 1: Synthesis of Compound 1a

[0112] Synthesis of compound 26:

[0113]

[0114] In a 500 ml round bottom flask, add deionized water 24 g and K2CO3 0.2 g, stir for 10 min, add dry THF 40 g, stir for another 30 min, then add the compound shown in formula 28 (4.8 g, 0.04 mol) by syringe dropwise at normal pressure, stir at room temperature for 36 h. Extract three times with dichloromethane (15 mL), collect the upper organic layer and dry over MgSO4 overnight. Filter the solution to remove MgSO4, and remove the solvent with a rotary evaporator to obtain 10.0 g of the compound shown in formula 26, with a yield of 93%.

[0115] Synthesis of compound of formula 25:

[0116]

[0117] In a 500 ml round bottom flask, add deionized water 24 g and K2CO3 0.2 g, stir for 10 min, add dry THF 40 g, stir for another 30 min, then add the compound shown in formula 28 (4.8 g, 0.04 mol) by syringe dropwise at normal pressure, stir at room temperature for 36 h. Extract three times with dichloromethane (15 mL), collect the upper organic layer and dry over MgSO4 overnight. Filter the solution to remove MgSO4, and remove the solvent with a rotary evaporator to obtain 10.0 g of the compound shown in formula 26, with a yield of 93%.

[0118] Synthesis of compound of formula 24:

[0119]

[0120] In a 500 ml round bottom flask, add deionized water 24 g and K2CO3 0.2 g, stir for 10 min, add dry THF 40 g, stir for another 30 min, then add the compound shown in formula 28 (4.8 g, 0.04 mol) by syringe dropwise at normal pressure, stir at room temperature for 36 h. Extract three times with dichloromethane (15 mL), collect the upper organic layer and dry over MgSO4 overnight. Filter the solution to remove MgSO4, and remove the solvent with a rotary evaporator to obtain 10.0 g of the compound shown in formula 26, with a yield of 93%.

[0121] Synthesis of compound of formula 1a-1:

[0122]

[0123] To the compound of formula 24, 6.43 g (0.01 mol) was added the compound of formula 6, 1.72 g, acetonitrile, 100 ml, triethylamine, 0.3 g, in a three-necked flask, nitrogen was bubbled to replace the air, an ice water bath was added, Pd(OAc)2, 0.2 g, tris(o-tolyl)phosphine, was added, and the reaction was stirred at reflux for 1 h. After the reaction was completed, the reaction mixture was filtered, and the filtrate was distilled to obtain the compound of formula 1a-1, 7.66 g, in a yield of 83.5%.

[0124] Synthesis of the compound of formula 1a:

[0125]

[0126] To the compound of formula 1a-1, 9.17 g (0.01 mol) was added a 200 ml beaker, and mechanical stirring was performed. After the compound was dissolved in 10 ml of concentrated hydrochloric acid, the reaction temperature was lowered to 0-4°C, and sodium nitrite aqueous solution, which was prepared by dissolving 1.38 g of sodium nitrite in 5 ml of water, and sodium azide solution, which was prepared by dissolving 1.56 g of sodium azide in 5 ml of water, were sequentially added. The reaction was performed for 1.5 h, and after the reaction was completed, the reaction mixture was filtered and washed with water. The compound of formula 1a, 8.46 g, was obtained in a yield of 85% by recrystallization with acetone.

[0127] Example 2, Synthesis of the compound of formula 1b

[0128] Synthesis of the compound of formula 29:

[0129]

[0130] In a 500 ml round bottom flask, deionized water, 24 g, and K2CO3, 0.2 g, were added, and stirring was performed for 10 min. Dry THF, 40 g, was added, and stirring was further performed for 30 min. Then, the compound of formula 31 (5.37 g, 0.04 mol) was added dropwise by a syringe at normal pressure, and stirring was performed at room temperature for 36 h. The upper organic layer was collected by extracting with dichloromethane (15 mL) three times, and dried over MgSO4overnight. The solution was filtered to remove MgSO4, and the solvent was removed using a rotary evaporator to obtain the compound of formula 29, 11.18 g, in a yield of 90%.

[0131] Synthesis of the compound of formula 28:

[0132]

[0133] In a 500 ml round bottom flask, add 24 g of deionized water and 0.2 g of K2CO3, stir for 10 min, add 40 g of dry THF, stir for another 30 min, then add the compound shown in formula 28 (6.5 g, 0.02 mol) by syringe dropwise under normal pressure, stir at room temperature for 36 h. Finally, add 4.34 g (0.08 mol) of trimethylchlorosilane, cap, extract with dichloromethane (15 mL) three times, collect the upper organic layer and dry over MgSO4 overnight. Filter the solution to remove MgSO4, and remove the solvent on a rotary evaporator to obtain 11.0 g of the compound shown in formula 27 with a yield of 93%.

[0134] Synthesis of compound of formula 27:

[0135]

[0136] In a 500 ml round bottom flask, add 24 g of deionized water and 0.2 g of K2CO3, stir for 10 min, add 40 g of dry THF, stir for another 30 min, then add the compound shown in formula 28 (6.5 g, 0.02 mol) by syringe dropwise under normal pressure, stir at room temperature for 36 h. Finally, add 4.34 g (0.08 mol) of trimethylchlorosilane, cap, extract with dichloromethane (15 mL) three times, collect the upper organic layer and dry over MgSO4 overnight. Filter the solution to remove MgSO4, and remove the solvent on a rotary evaporator to obtain 11.0 g of the compound shown in formula 27 with a yield of 93%.

[0137] Synthesis of compound of formula 1b-1:

[0138]

[0139] Take 7.21 g (0.01 mol) of the compound shown in formula 27, add 3.44 g of the compound shown in formula 6, add 100 ml of acetonitrile, add 0.3 g of triethylamine, add to a three-necked flask, replace the air with nitrogen by bubbling, add an ice water bath, add 0.2 g of Pd(OAc)2, and 3 (o-tolyl) phosphine, stir and reflux for 1 h, filter after the reaction is complete, and distill to obtain 17.52 g of the compound shown in formula 1b-1 with a yield of 83%.

[0140] Synthesis of compound of formula 1b:

[0141]

[0142] To the compound of formula 1b-1 17.49 g (0.01 mol) was added to a 200 ml beaker, mechanically stirred, after dissolving with 10 ml of concentrated hydrochloric acid, the reaction temperature was lowered to 0-4°C, 2.76 g of sodium nitrite dissolved in 10 ml of water was added to prepare a solution, 3.12 g of sodium azide dissolved in 10 ml of water was added to prepare a solution, and the reaction was stirred for 1.5 h. After the reaction was completed, it was filtered with water and washed with acetone to obtain 16.0 g of the compound of formula 1b with a yield of 84%.

[0143] Example 3, Synthesis of the compound of formula 1c

[0144] Synthesis of the compound of formula 32:

[0145]

[0146] In a 500 ml round bottom flask, 24 g of deionized water and 0.2 g of K2CO3 were added and stirred for 10 min, 40 g of dry THF was added, and then stirred for another 30 min, then 7.92 g of the compound of formula 33, 0.06 mol, was added by syringe dropwise at normal pressure, and stirred at room temperature for 36 h. Finally, 4.34 g of trimethylchlorosilane (0.08 mol) was added, capped, extracted with dichloromethane (15 mL) three times, and the upper organic layer was collected and dried over MgSO4 overnight. The solution was filtered to remove MgSO4, and most of the solvent was removed by a rotary evaporator to obtain 6.37 g of the compound of formula 32 with a yield of 94%.

[0147] Synthesis of the compound of formula 1c-1:

[0148]

[0149] To the compound of formula 32 6.79 g (0.01 mol), the compound of formula 6 3.44 g was added, acetonitrile 100 ml was added, triethylamine 0.3 g was added, and it was added to a three-necked flask, nitrogen was bubbled to replace the air, an ice water bath was added, Pd(OAc)2 0.2 g, tris(o-tolyl)phosphine were added, and the reaction was stirred at reflux for 1 h. After the reaction was completed, it was filtered and distilled to obtain 10.42 g of the compound of formula 1c-1 with a yield of 85%.

[0150] Synthesis of the compound of formula 1c:

[0151]

[0152] Take the compound 12.25 g (0.01 mol) shown in formula 1c-1 into a 200 ml beaker, mechanically stir, add 10 ml of concentrated hydrochloric acid to dissolve, and then cool the reaction temperature to 0-4℃, add the solution of 2.76 g of sodium nitrite dissolved in 10 ml of water, and the solution of 3.12 g of sodium azide dissolved in 10 ml of water in turn, react for 1.5 h, filter and wash with water after the reaction is completed, and recrystallize with acetone to obtain 11.19 g of the compound shown in formula 1c, with a yield of 81%.

[0153] Example 4, synthesis of the compound shown in formula 2a

[0154] Synthesis of the compound shown in formula 35:

[0155]

[0156] In a 500 ml round bottom flask, add 24 g of deionized water and 0.2 g of K2CO3, stir for 10 min, add 40 g of dry THF, and then stir for another 30 min, and then add the compound shown in formula 37 8.88 g, 0.06 mol, and the compound shown in formula 38 8.16 g, 0.06 mol, drop by drop through a syringe at normal pressure, and stir at room temperature for 36 h. Extract three times with dichloromethane (15 mL), collect the upper organic layer and dry over MgSO4 overnight. Filter the solution to remove MgSO4, and remove the solvent with a rotary evaporator to obtain 4.89 g of the compound shown in formula 35, with a yield of 92%.

[0157] Synthesis of the compound shown in formula 36

[0158]

[0159] In a 500 ml round bottom flask, add 24 g of deionized water and 0.2 g of K2CO3, stir for 10 min, add 40 g of dry THF, and then stir for another 30 min, and then add the compound shown in formula 38 8.16 g, 0.06 mol, drop by drop through a syringe at normal pressure, and stir at room temperature for 36 h. Extract three times with dichloromethane (15 mL), collect the upper organic layer and dry over MgSO4 overnight. Filter the solution to remove MgSO4, and remove the solvent with a rotary evaporator to obtain 4.60 g of the compound shown in formula 36, with a yield of 93%.

[0160] Synthesis of the compound shown in formula 34:

[0161]

[0162] In a 500 ml round bottom flask, add 24 g of deionized water and 0.2 g of K2CO3, stir for 10 min, add 40 g of dry THF, stir for another 30 min, then add 5.31 g of the compound shown in Figure 35, 0.01 mol, 4.95 g of the compound shown in Figure 36, 0.01 mol, by syringe dropwise at room temperature, stir for 36 h, finally add 4.34 g of trimethylchlorosilane (0.04 mol), cap, extract with dichloromethane (15 mL) three times, collect the upper organic layer and dry over MgSO4 overnight. The solution is filtered to remove MgSO4, and the solvent is removed on a rotary evaporator to obtain 7.63 g of the compound shown in Figure 34, with a yield of 87%.

[0163] Synthesis of the compound shown in Figure 2a-1:

[0164]

[0165] Take 11.66 g (0.01 mol) of the compound shown in Figure 34, add 1.72 g of the compound shown in Figure 6, add 100 ml of acetonitrile, add 0.3 g of triethylamine, add to a three-necked flask, replace the air with nitrogen by bubbling, add an ice water bath, add 0.2 g of Pd(OAc)2, and 3 (o-tolyl) phosphine, stir and reflux for 1 h, filter after the reaction is complete, and distill to obtain 11.95 g of the compound shown in Figure 2a-1, with a yield of 83%.

[0166] Synthesis of the compound shown in Figure 2a:

[0167]

[0168] Take 14.37 g (0.01 mol) of the compound shown in Figure 2a-1, add to a 200 ml beaker, mechanically stir, add 10 ml of concentrated hydrochloric acid after dissolving, cool the reaction temperature to 0-4℃, add 1.38 g of sodium nitrite solution prepared by dissolving sodium nitrite in 5 ml of water, and 1.56 g of sodium azide solution prepared by dissolving sodium azide in 5 ml of water, in sequence, react for 1.5 h, filter and wash with water after the reaction is complete, recrystallize with acetone to obtain 12.58 g of the compound shown in Figure 2a, with a yield of 83%.

[0169] Example 5, Synthesis of the compound shown in Figure 2b

[0170] Synthesis of the compound shown in Figure 40:

[0171]

[0172] In a 500 ml round bottom flask was added 24 g of deionized water and 0.2 g of K2CO3, stirred for 10 min, added 40 g of dry THF, stirred for another 30 min, then added 8.88 g of compound 37, 0.06 mol, by syringe dropwise at normal pressure, stirred for 36 h at room temperature. Extracted three times with dichloromethane (15 mL), collected the upper organic layer and dried over MgSO4overnight. The solution was filtered to remove MgSO4, and the solvent was removed by a rotary evaporator to obtain 5.05 g of compound 40, with a yield of 89%.

[0173] Synthesis of compound 41:

[0174]

[0175] In a 500 ml round bottom flask was added 24 g of deionized water and 0.2 g of K2CO3, stirred for 10 min, added 40 g of dry THF, stirred for another 30 min, then added 8.88 g of compound 37, 0.06 mol, by syringe dropwise at normal pressure, stirred for 36 h at room temperature. Extracted three times with dichloromethane (15 mL), collected the upper organic layer and dried over MgSO4overnight. The solution was filtered to remove MgSO4, and the solvent was removed by a rotary evaporator to obtain 5.05 g of compound 40, with a yield of 89%.

[0176] Synthesis of compound 39:

[0177]

[0178] In a 500 ml round bottom flask was added 24 g of deionized water and 0.2 g of K2CO3, stirred for 10 min, added 40 g of dry THF, stirred for another 30 min, then added 8.88 g of compound 37, 0.06 mol, by syringe dropwise at normal pressure, stirred for 36 h at room temperature. Extracted three times with dichloromethane (15 mL), collected the upper organic layer and dried over MgSO4overnight. The solution was filtered to remove MgSO4, and the solvent was removed by a rotary evaporator to obtain 5.05 g of compound 40, with a yield of 89%.

[0179] Synthesis of compound 2b-1:

[0180]

[0181] Take the compound shown in formula 39 12.02 g (0.01 mol), add the compound shown in formula 6 3.44 g, add acetonitrile 100 ml, add triethylamine 0.3 g, add a three-necked flask, replace the air with nitrogen by bubbling, add an ice water bath, add Pd(OAc)2 0.2 g, tris (o-tolyl) phosphine, heat to reflux and stir for 1 h. After the reaction is completed, filter and distill to obtain the compound shown in formula 2b-1 13.82 g, with a yield of 79%.

[0182] Synthesis of the compound shown in formula 2b:

[0183]

[0184] Take the compound shown in formula 2b-1 17.49 g (0.01 mol) and add it to a 200 ml beaker. Stir mechanically, add 10 ml of concentrated hydrochloric acid, and then cool the reaction temperature to 0-4°C. Add a solution of 2.76 g of sodium nitrite dissolved in 10 ml of water, and then add a solution of 3.12 g of sodium azide dissolved in 10 ml of water. Stir for 1.5 h. After the reaction is completed, filter and wash with water. Recrystallize from acetone to obtain the compound shown in formula 2b 17.34 g, with a yield of 91%.

[0185] Example 6, Synthesis of the compound shown in formula 2c

[0186] Synthesis of the compound shown in formula 42:

[0187]

[0188] In a 500 ml round-bottom flask, add 24 g of deionized water and 0.2 g of K2CO3, stir for 10 min, add 40 g of dry THF, and then stir for another 30 min. Then, at normal pressure, add the compound shown in formula 35 10.06 g (0.02 mol) dropwise through a syringe, and stir at room temperature for 36 h. Finally, add 4.34 g (0.04 mol) of trimethylchlorosilane, cap, extract with dichloromethane (15 mL) three times, collect the upper organic layer, and dry over MgSO4 overnight. Filter the solution to remove MgSO4, and remove the solvent on a rotary evaporator to obtain the compound shown in formula 42 9.26 g, with a yield of 77%.

[0189] Synthesis of the compound shown in formula 2c-1:

[0190]

[0191] Take the compound shown in formula 42 12.02 g (0.01 mol), add the compound shown in formula 6 3.44 g, add acetonitrile 100 ml, add triethylamine 0.3 g, add a three-necked flask, replace the air with nitrogen by bubbling, add an ice water bath, add Pd(OAc)2 0.2 g, tris (o-tolyl) phosphine, heat to reflux and stir for 1 h. After the reaction is completed, filter and distill to obtain the compound shown in formula 2c-1 13.29 g, with a yield of 76%.

[0192] Synthesis of the compound shown in formula 2c:

[0193]

[0194] Take the compound shown in formula 2c-1 17.49 g (0.01 mol) and add it to a 200 ml beaker. Stir mechanically, add 10 ml of concentrated hydrochloric acid, and then cool the reaction temperature to 0-4°C. Add a solution of 2.76 g of sodium nitrite dissolved in 10 ml of water, and then add a solution of 3.12 g of sodium azide dissolved in 10 ml of water. Stir for 1.5 h. After the reaction is completed, filter and wash with water. Recrystallize from acetone to obtain the compound shown in formula 2c 15.62 g, with a yield of 82%.

[0195] Example 7, synthesis of the compound shown in formula 3a

[0196] Synthesis of the compound shown in formula 44:

[0197]

[0198] In a 500 ml round-bottom flask, add 24 g of deionized water and 0.2 g of K2CO3, stir for 10 min, add 40 g of dry THF, and then stir for another 30 min. Then, at normal pressure, add 1.48 g of the compound shown in formula 37, 0.01 mol, 1.52 g of the compound shown in formula 46, 0.01 mol, and 1.36 g of the compound shown in formula 38, 0.01 mol, by dropping them through a syringe. Stir at room temperature for 36 h. Extract three times with dichloromethane (15 mL), collect the upper organic layer, and dry over MgSO4 overnight. Filter the solution to remove MgSO4, and remove the solvent on a rotary evaporator to obtain the compound shown in formula 44 6.59 g, with a yield of 87%.

[0199] Synthesis of the compound shown in formula 45:

[0200]

[0201] In a 500 ml round bottom flask, add 24 g of deionized water and 0.2 g of K2CO3, stir for 10 min, add 40 g of dry THF, stir for another 30 min, then add 1.52 g of the compound shown in formula 46, 0.01 mol, 2.72 g of the compound shown in formula 38, 0.02 mol, at room temperature, stir for 36 h. Extract three times with dichloromethane (15 mL), collect the upper organic layer and dry over MgSO4 overnight. Filter the solution to remove MgSO4, and remove the solvent with a rotary evaporator to obtain 5.77 g of the compound shown in formula 45, with a yield of 85%.

[0202] Synthesis of compound of formula 43:

[0203]

[0204] In a 500 ml round bottom flask, add 24 g of deionized water and 0.2 g of K2CO3, stir for 10 min, add 40 g of dry THF, stir for another 30 min, then add 1.52 g of the compound shown in formula 46, 0.01 mol, 2.72 g of the compound shown in formula 38, 0.02 mol, at room temperature, stir for 36 h. Finally, add 12.96 g of trimethylchlorosilane (0.12 mol), cap, extract three times with dichloromethane (15 mL), collect the upper organic layer and dry over MgSO4 overnight. Filter the solution to remove MgSO4, and remove the solvent with a rotary evaporator to obtain 15.54 g of the compound shown in formula 43, with a yield of 92%.

[0205] Synthesis of compound of formula 3a-1

[0206]

[0207] Take 16.89 g of the compound shown in formula 43 (0.01 mol), add 1.72 g of the compound shown in formula 6, add 100 ml of acetonitrile, add 0.3 g of triethylamine, add to a three-necked flask, replace the air with nitrogen by bubbling, add an ice water bath, add 0.2 g of Pd(OAc)2, and 3 (o-tolyl) phosphine, stir the reaction at reflux for 1 h, filter after the reaction is complete, and distill to obtain 16.20 g of the compound shown in 3a-1, with a yield of 82.6%.

[0208] Synthesis of compound of formula 3a:

[0209]

[0210] Take the compound shown in formula 3a-1 19.62g (0.01mol) into 200ml beaker, mechanical stirring, after dissolving with 10ml concentrated hydrochloric acid, cooling reaction temperature 0-4℃, in turn add 1.38g sodium nitrite solution prepared by dissolving sodium nitrite in 5ml water, 1.56g sodium azide solution prepared by dissolving sodium azide in 5ml water, reaction 3h, after reaction completion, filter water washing, acetone recrystallization, get compound shown in formula 3a 17.15g, yield 84%.

[0211] Example 8, synthesis of compound shown in formula 3b

[0212] Synthesis of compound shown in formula 48

[0213]

[0214] In 500ml round bottom flask, add 24g of deionized water and 0.2g of K2CO3, stir for 10min, add 40g of dry THF, stir for another 30min, then add 8.88g of compound shown in formula 37, 8.88mol, 4.56g of compound shown in formula 46, 0.03mol, by syringe dropwise, stir at room temperature for 36h. Extracted with dichloromethane (15mL) three times, collect the upper organic layer and dry over MgSO4 overnight. The solution is filtered to remove MgSO4, and the solvent is removed by rotary evaporator to obtain 10.8g of compound shown in formula 35, with a yield of 84%.

[0215] Synthesis of compound shown in formula 47

[0216]

[0217] In 500ml round bottom flask, add 24g of deionized water and 0.2g of K2CO3, stir for 10min, add 40g of dry THF, stir for another 30min, then add 7.93g of compound shown in formula 48, 0.01mol, 7.21g of compound shown in formula 38, 0.01mol, by syringe dropwise, stir at room temperature for 36h. Finally, add 6.48g of trimethylchlorosilane (0.6mol), cap, extract with dichloromethane (15mL) three times, collect the upper organic layer and dry over MgSO4 overnight. The solution is filtered to remove MgSO4, and the solvent is removed by rotary evaporator to obtain 14.66g of compound shown in formula 47, with a yield of 85%.

[0218] Synthesis of compound shown in formula 3b-1

[0219]

[0220] Take the compound shown in formula 47 17.25 g (0.01 mol), add the compound shown in formula 6 3.44 g, add acetonitrile 100 ml, add triethylamine 0.3 g, add a three-necked flask, replace the air with nitrogen by bubbling, add an ice water bath, add Pd(OAc)2 0.2 g, tris (o-tolyl) phosphine, heat to reflux and stir for 1 h. After the reaction is completed, filter and distill to obtain the compound shown in formula 3b-1 18.4 g, with a yield of 81%.

[0221] Synthesis of the compound shown in formula 3b

[0222]

[0223] Take the compound shown in formula 3b-1 22.72 g (0.01 mol) and add it to a 200 ml beaker. Stir mechanically, add 10 ml of concentrated hydrochloric acid, and then dissolve it. Cool the reaction temperature to 0-4°C, and then add a solution of 2.76 g of sodium nitrite dissolved in 10 ml of water, and a solution of 3.12 g of sodium azide dissolved in 10 ml of water. React for 2 h. After the reaction is completed, filter and wash with water. Recrystallize from acetone to obtain the compound shown in formula 3b 20.88 g, with a yield of 86%.

[0224] Example 9, Synthesis of the compound shown in formula 3C

[0225] Synthesis of the compound shown in formula 49:

[0226]

[0227] In a 500 ml round-bottom flask, add 24 g of deionized water and 0.2 g of K2CO3, stir for 10 min, add 40 g of dry THF, and then stir for another 30 min. Then, at normal pressure, add the compound shown in formula 44 15.14 g, 0.02 mol, by dropping it through a syringe, and stir at room temperature for 36 h. Finally, add 6.48 g (0.06 mol) of trimethylchlorosilane, cap it, extract it with dichloromethane (15 mL) three times, collect the upper organic layer, and dry it over MgSO4 overnight. Filter the solution to remove MgSO4, and remove the solvent on a rotary evaporator to obtain the compound shown in formula 49 11.21 g, with a yield of 65%.

[0228] Synthesis of the compound shown in formula 3C-1:

[0229]

[0230] Take the compound shown in formula 49 17.25g (0.01mol), add the compound shown in formula 6 3.44g, add acetonitrile 100ml, add triethylamine 0.3g, add a three-necked flask, nitrogen bubble replacement air, add ice water bath, add Pd (OAc) 20.2g, tri (o-tolyl) phosphine, heat reflux stirring reaction 1h, after reaction, filter, distillation to obtain the compound shown in formula 3C-1 17.95g, yield 79%.

[0231] Synthesis of the compound shown in formula 3C:

[0232]

[0233] Take the compound shown in formula 3C-1 22.72g (0.01mol) into 200ml beaker, mechanical stirring, add 10ml concentrated hydrochloric acid after dissolution, cooling reaction temperature 0-4℃, add 2.76g sodium nitrite dissolved in 10ml water to prepare the solution, 3.12g sodium azide dissolved in 10ml water to prepare the solution, reaction 2h, after reaction, filter water, acetone recrystallization, to obtain the compound shown in formula 3C 20.64g, yield 85%.

[0234] Example 10, the compound shown in formula 1C as photosensitizer

[0235] Dissolve the compound shown in formula 1C in dichloromethane, add benzocyclobutene resin solution, stir evenly, get negative photosensitive benzocyclobutene resin (the mass ratio of compound shown in formula 1C and benzocyclobutene resin is 5:95). The prepared solution is spin coated on a silicon wafer, dried after soft baking, and then exposed to light in a mask plate on a photoetching machine. The effect after exposure and development is shown in Figure 1 , with a resolution of 13 microns.

[0236] The above has been described in detail. For those skilled in the art, without departing from the purpose and scope of the present application, and without unnecessary experiments, the present application can be implemented in a wide range of equivalent parameters, concentrations and conditions. Although the present application gives a special example, it should be understood that further improvement can be made to the present application. In short, according to the principle of the present application, this application intends to include any change, use or improvement of the present application, including the change made by the conventional technology known in the art, which is out of the range disclosed in this application.

Claims

1. A compound represented by formula (1), formula (2) or formula (3): wherein x, y represent any value from 1 to 10; R5 represents a capping group, which is any one of trimethylchlorosilane, dimethylvinylchlorosilane, dimethylphenylchlorosilane after removing chlorine. In equations (1), (2), and (3), R1, R2, R3, and R4 independently represent hydrogen atoms and C1-C atoms. 10 Straight-chain or branched alkyl groups, mercapto groups, substituted or unsubstituted aromatic groups, C2-C 10 alkenyl, , express The integers n = 1-3, and at least one of R1, R2, R3, and R4 is a ; In formula (4), R2, R3, R4, R5, x, y are defined as R2, R3, R4, R5, x, y in formula (1). The acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid; 2. The compound of claim 1, wherein R1, R2, R3, and R4 each independently represent a hydrogen atom, a C1-C6 straight-chain or branched alkyl group, a mercapto group, a phenyl group, or a C2-C6 alkenyl group. , express The integers n = 1-3, and at least one of R1, R2, R3, and R4 is a .

3. A process for the preparation of a compound of formula (1) as depicted in claim 1, wherein, R1 is comprising the steps of dissolving a compound represented by formula (4) in an acid solution, cooling to a reaction temperature, sequentially adding an aqueous sodium nitrite solution and an aqueous sodium azide solution, after the reaction is completed, performing suction filtration and washing with water, and recrystallizing from acetone to obtain a compound represented by formula (1), The molar ratio of the compound represented by formula (4) to sodium nitrite and sodium azide is 1:1-2:1-2, respectively.

4. The method of claim 3, wherein, The reaction temperature is 0-10℃. The reaction time is 0.2-3h. The compound represented by formula (4) is prepared by a method comprising the following steps: The compound represented by formula (5) and the compound represented by formula (6) are dissolved in an organic solvent, a palladium catalyst, a ligand, a base are added, and a Heck reaction is performed to obtain the compound represented by formula (4).

5. The method of claim 3, wherein, In formula (5), R2, R3, R4, R5, x, y are defined as R2, R3, R4, R5, x, y in formula (1). The palladium catalyst is Pd(OAc)2 or Pd(PPh3)4. The base is selected from at least one of potassium carbonate, sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium bicarbonate, and triethylamine.

6. The method of claim 5, wherein, The ligand is tri (o-tolyl) phosphine. The temperature of the Heck reaction is 60-120℃, and the time is 0.2-5h. In formula (11), R2, R3, R4, R5, x, y are defined as R2, R3, R4, R5, x, y in formula (2). The compound represented by formula (19) is dissolved in an acid solution, cooled to a reaction temperature, and then sodium nitrite aqueous solution and sodium azide aqueous solution are added successively, after the reaction is completed, water washing is performed by suction filtration, and acetone recrystallization is performed to obtain the compound represented by formula (3).

7. A process for the preparation of a compound of formula (2) as depicted in claim 1, wherein, R1 is comprising the steps of: dissolving a compound shown in formula (11) in an acid solution, reducing the reaction temperature, sequentially adding an aqueous sodium nitrite solution and an aqueous sodium azide solution, after the reaction is completed, performing suction filtration and water washing, and recrystallizing with acetone to obtain a compound shown in formula (2), In formula (19), R2, R3, R4, R5, x, y are defined as R2, R3, R4, R5, x, y in formula (3).

8. A process for preparing a compound of formula (3) as shown in claim 1, wherein, R1is comprising the steps of:

9. Use of the compound represented by formula (1), formula (2) or formula (3) in claim 1 as a photo-crosslinking agent in the preparation of a photo-crosslinking material. ​ ​

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