A bio-based light-regulated detachable anti-adhesion glue and a preparation method thereof

Abstract

The present application belongs to the technical field of preparation of viscosity-reducing glue, and particularly relates to a bio-based light-regulated detachable viscosity-reducing glue and a preparation method thereof. A coumarin chain extender is prepared through a reversible light cyclization reaction of a coumarin monomer, and then a light-regulated detachable viscosity-reducing glue base glue is synthesized through a chain extension reaction of the coumarin chain extender and a prepolymer synthesized from a polyol and an isocyanate. Then, reinforcing fillers and a silane coupling agent are added to the system to uniformly disperse the reinforcing fillers in the light-regulated detachable viscosity-reducing glue, so as to guarantee the mechanical properties such as tensile strength, peel strength and hardness of the light-regulated detachable viscosity-reducing glue. The light-regulated detachable viscosity-reducing glue can achieve the purpose of being detachable through irradiation of ultraviolet light of a fixed wave band, and has the advantage of controllable bonding strength. The light-regulated detachable viscosity-reducing glue not only has the performance of being light-regulated and detachable, but also is prepared from bio-based raw materials, which is conducive to the sustainable development of the ecological environment, and is mainly suitable for wafer manufacturing and processing and chip manufacturing industries.

Description

Technical Field

[0001] This invention belongs to the field of anti-adhesive adhesive preparation technology, specifically relating to a bio-based light-controlled detachable anti-adhesive adhesive and its preparation method. Background Technology

[0002] UV-resistant adhesives are a type of adhesive that exhibits high adhesion and bonding strength under normal conditions, but whose adhesion strength drops sharply after a short period of ultraviolet (UV) irradiation and is easy to peel off. They are widely used in wafer processing, semiconductor chips, transistors, integrated circuits, optical microscopes and other fields, and play a very important role in fixing.

[0003] Existing UV-resistant adhesives often require prolonged irradiation and tend to leave residue after peeling. This is typically due to the use of a main adhesive combined with photosensitive monomer resins, which fails to achieve effective fixation and easy pickup. Furthermore, adhesives are often referred to as "industrial MSG" due to numerous environmental problems caused by harmful substances such as toxic solvents, additives, and volatile organic compounds. Therefore, it is necessary to develop a resistant adhesive with high peeling efficiency, no residue after peeling, no environmental pollution, no threat to human health, and a simple preparation method. Summary of the Invention

[0004] This invention proposes a UV-resistant adhesive that is harmless to humans and the environment, has high peeling efficiency, and leaves no residue, as well as its preparation method. Through the synergistic effect of reinforcing materials, silane coupling agents, and bio-based photo-regulated removable adhesive prepolymers, the reinforcing materials are uniformly dispersed within the adhesive prepolymers, which is beneficial for achieving a more complete crosslinking density and increasing the strength between chemical bonds. This greatly improves the mechanical properties of the adhesive and solves the problem of low peeling force in most UV-resistant adhesives.

[0005] The present invention adopts the following technical solution:

[0006] The bio-based, light-controlled, detachable, non-stick adhesive is prepared by the stepwise polymerization of isocyanate, polyol, and coumarin chain extender, followed by the addition of reinforcing materials and silane coupling agents. The reaction equation is as follows:

[0007]

[0008] The specific preparation steps of the bio-based light-controlled detachable anti-adhesive adhesive are as follows:

[0009] (1) Coumarin chain extenders were prepared by irradiating 7-hydroxycoumarin or 4-methylumbelliferone with UV light for 3 hours.

[0010] (2) Add isocyanate to a nitrogen-filled three-necked flask and dissolve it with an organic solvent. Then add polyol and organotin catalyst and stir at 60-80℃ for 2 hours to obtain a viscous and transparent prepolymer MU-1.

[0011] The isocyanate is one of isophorone diisocyanate, 2,4-toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.

[0012] The polyol is one of the following: polytetrahydrofuran diol, polyethylene adipate, polybutylene adipate, polycaprolactone diol, polytetrahydrofuran ether diol, polypropylene glycol, polyethylene glycol, or polylactic acid.

[0013] The organotin catalyst is either dibutyltin dilaurate or stannous octoate; its addition amount is 0.5% of the mass of the isocyanate.

[0014] The molar ratio of isocyanate to polyol is 1.04:1.

[0015] (3) Add coumarin chain extender soluble in organic solvent to the prepolymer, and carry out chain extension reaction at 30-40℃ for 1h to obtain viscous prepolymer MU-2.

[0016] The molar ratio of coumarin chain extender to isocyanate is 2:1.

[0017] (4) Add the reinforcing material to the organic solvent and stir thoroughly to disperse it. Then add it to MU-2 along with the silane coupling agent. Stir the system at 30-40℃ for 2 hours to obtain the bio-based light-controlled detachable adhesive.

[0018] The reinforcing material is one of nano-calcium carbonate, silicon dioxide, carbon black, or short fiber, and its addition amount is 0.3-2 times the mass of isocyanate.

[0019] The silane coupling agent is one or more of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, vinyltris(b-methoxyethoxy)silane, and 3-aminopropyltrimethoxysilane, and its addition amount is 1% of the mass of the polyol.

[0020] The organic solvent used in each of the above steps is one of N,N-dimethylformamide, acetone, ethyl acetate, butyl acetate, toluene, xylene, dichloromethane, and tetrahydrofuran.

[0021] This invention prepares a coumarin chain extender via a reversible photocyclization reaction of coumarin monomers. The resulting anti-adhesive adhesive can be disassembled by irradiation with ultraviolet light of a fixed wavelength, offering the advantage of controllable adhesive strength. This bio-based, photo-controlled, disassembled anti-adhesive adhesive can be applied in wafer fabrication and other fields, significantly reducing the time required for peeling and improving production efficiency, demonstrating high application value. Furthermore, this anti-adhesive adhesive is prepared using bio-based raw materials such as coumarin monomers, offering advantages in environmental friendliness and contributing to sustainable ecological development.

[0022] Beneficial effects:

[0023] This invention utilizes the synergistic effect of reinforcing materials, silane coupling agents, and bio-based photo-regulated removable adhesive prepolymers to uniformly disperse the reinforcing materials within the adhesive prepolymer. This facilitates a more complete crosslinking density and increases the strength between chemical bonds, significantly improving the mechanical properties of the adhesive and solving the problem of low peel strength in most UV adhesives. Furthermore, based on the excellent mechanical properties of the adhesive, a coumarin chain extender is prepared through a reversible photocyclization reaction of coumarin monomers. This allows the adhesive to achieve removability under fixed-wavelength 254nm UV irradiation, offering the advantage of controllable adhesive strength.

[0024] The bio-based, light-controlled, detachable adhesive of this invention can be applied to wafer processing and other fields, which can greatly reduce the time required for peeling, improve production efficiency, and has extremely high application value. Furthermore, this adhesive is prepared using bio-based raw materials such as coumarin chain extenders, which has the advantages of being green and environmentally friendly, and is conducive to the sustainable development of the ecological environment. Attached Figure Description

[0025] Figure 1 The infrared spectrum of the bio-based photomodulated removable adhesive prepared by using polytetrahydrofuran diol as a polyol, 2,4-toluene diisocyanate as an isocyanate, and coumarin chain extension in Example 1 is shown.

[0026] Figure 2 Thermogravimetric analysis (TGA) of the bio-based photomodulated detachable adhesive prepared using polytetrahydrofuran diol as the polyol, 2,4-toluene diisocyanate as the isocyanate, and self-made coumarin chain extension in Example 1.

[0027] Figure 3 The thermogravimetric rate diagram of the bio-based photomodulated detachable adhesive prepared by using polytetrahydrofuran diol as a polyol, 2,4-toluene diisocyanate as an isocyanate, and coumarin chain extension in Example 1 is shown.

[0028] Figure 4 This is a comparison chart of the tensile strength of Examples 1-15 and Comparative Examples 1-2.

[0029] Figure 5This is a comparison chart of the elongation at break of Examples 1-15 and Comparative Examples 1-2.

[0030] Figure 6 The figures show a comparison of peel strength before and after UV light-induced adhesion reduction in Examples 1-15 and Comparative Examples 1-2. Detailed Implementation

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0032] Example 1

[0033] Take 20g of 4-methylumbelliferone dissolved in 30ml of N,N-dimethylformamide in a beaker, and irradiate with 350nm UV light for 3h to prepare coumarin chain extender. 6.94 g of 2,4-toluene diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. 4.39 g of polytetrahydrofuran glycol and 0.0347 g of dibutyltin dilaurate were then added, and the mixture was stirred at 75 °C for 2 h to obtain a viscous and transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. 2.38 g of nano-calcium carbonate mixed with 20 ml of N,N-dimethylformamide and 0.2 g of γ-(2,3-epoxypropoxy)propyltrimethoxysilane were simultaneously added to the reaction system, and the mixture was stirred at 40 °C for 2 h to obtain a bio-based, light-controlled, detachable, non-stick adhesive.

[0034] According to GB / T2792-1998, the test method for 180° peel strength of adhesives was used. The sample width was 25 mm, the length was 200 mm, and the tensile rate was 300 mm / min. The peel strength was measured to be 20 N / 25 mm. After 15 min of 254 nm UV irradiation, the peel strength was 0.3 N / 25 mm. The prepared product was tested according to ASTM D882, with a test speed of 500 mm / min. The tensile strength was 12.34 MPa, and the elongation at break was 310%. The residual adhesive rate was measured to be 1 / 1450 by microscopic testing.

[0035] Example 2

[0036] The preparation of the coumarin chain extender is the same as in Example 1.

[0037] 6.94 g of isophorone diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. 7.9466 g of polyethylene adipate and 0.0347 g of dibutyltin dilaurate were then added, and the mixture was stirred at 75 °C for 2 h to obtain a viscous and transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. 2.38 g of nano-calcium carbonate mixed with 20 ml of N,N-dimethylformamide and 0.2 g of γ-(2,3-epoxypropoxy)propyltrimethoxysilane were simultaneously added to the reaction system, and the mixture was stirred at 40 °C for 2 h to obtain a bio-based, light-controlled, detachable, non-adhesive adhesive.

[0038] The peel strength was measured to be 19.5 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.5 N / 25 mm; the tensile strength was 11.37 MPa, and the elongation at break was 289%; the residual adhesive rate was measured to be 1 / 1293 by microscopic testing.

[0039] Example 3

[0040] The preparation of the coumarin chain extender is the same as in Example 1.

[0041] 6.94 g of isophorone diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. 7.3752 g of polybutylene adipate and 0.0347 g of dibutyltin dilaurate were then added, and the mixture was stirred at 75 °C for 2 h to obtain a viscous and transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. 2.38 g of nano-calcium carbonate mixed with 20 ml of N,N-dimethylformamide and 0.2 g of γ-methacryloyloxypropyltrimethoxysilane were added to the reaction system simultaneously, and the mixture was stirred at 40 °C for 2 h to obtain a bio-based photo-controlled detachable adhesive.

[0042] The peel strength was measured to be 19.4 N / 25 mm; after 15 min of 254 nm UV irradiation, the peel strength was 0.59 N / 25 mm; the tensile strength was 11.39 MPa, and the elongation at break was 279%; the residual adhesive rate was measured to be 1 / 1290 by microscopic testing.

[0043] Example 4

[0044] The preparation of the coumarin chain extender is the same as in Example 1.

[0045] 6.94 g of isophorone diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. 15.9 g of polycaprolactone diol and 0.0347 g of dibutyltin dilaurate were then added, and the mixture was stirred at 75 °C for 2 h to obtain a viscous and transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. 2.38 g of nano-calcium carbonate mixed with 20 ml of N,N-dimethylformamide and 0.2 g of γ-methacryloyloxypropyltrimethoxysilane were added to the reaction system simultaneously, and the mixture was stirred at 40 °C for 2 h to obtain a bio-based photo-controlled detachable adhesive.

[0046] The peel strength was measured to be 19.6 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.60 N / 25 mm; the tensile strength was 11.25 MPa, and the elongation at break was 288%; the residual adhesive rate was measured to be 1 / 1310 by microscopic testing.

[0047] Example 5

[0048] The preparation of the coumarin chain extender is the same as in Example 1.

[0049] 6.94 g of isophorone diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. 4.39 g of polytetrahydrofuran ether diol and 0.0347 g of dibutyltin dilaurate were then added, and the mixture was stirred at 75 °C for 2 h to obtain a viscous and transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. Nano-calcium carbonate (2.38 g) mixed with 20 ml of N,N-dimethylformamide and γ-methacryloyloxypropyltrimethoxysilane (0.2 g) were simultaneously added to the reaction system, and the mixture was stirred at 40 °C for 2 h to obtain a bio-based photo-controlled detachable adhesive.

[0050] The peel strength was measured to be 19.2 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.67 N / 25 mm; the tensile strength was 11.24 MPa, and the elongation at break was 267%; the residual adhesive rate was measured to be 1 / 1304 by microscopic testing.

[0051] Example 6

[0052] The preparation of the coumarin chain extender is the same as in Example 1.

[0053] 6.94 g of isophorone diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. 16.5 g of polypropylene glycol and 0.0347 g of dibutyltin dilaurate were then added, and the mixture was stirred at 75 °C for 2 h to obtain a viscous and transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. 2.38 g of nano-calcium carbonate mixed with 20 ml of N,N-dimethylformamide and 0.2 g of γ-mercaptopropyltriethoxysilane were added to the reaction system, and the mixture was stirred at 40 °C for 2 h to obtain a bio-based photo-controlled detachable adhesive.

[0054] The peel strength was measured to be 19.1 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.68 N / 25 mm; the tensile strength was 11.01 MPa, and the elongation at break was 260%; the residual adhesive rate was measured to be 1 / 1209 by microscopic testing.

[0055] Example 7

[0056] The preparation of the coumarin chain extender is the same as in Example 1.

[0057] 6.94 g of isophorone diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. 9 g of polyethylene glycol and 0.0347 g of dibutyltin dilaurate were then added, and the mixture was stirred at 75 °C for 2 h to obtain a viscous and transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. 2.38 g of nano-calcium carbonate mixed with 20 ml of N,N-dimethylformamide and 0.2 g of γ-mercaptopropyltriethoxysilane were simultaneously added to the reaction system, and the mixture was stirred at 40 °C for 2 h to obtain a bio-based, light-controlled, detachable, non-stick adhesive.

[0058] The peel strength was measured to be 19.33 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.69 N / 25 mm; the tensile strength was 10.90 MPa, and the elongation at break was 258%; the residual adhesive rate was measured to be 1 / 1302 by microscopic testing.

[0059] Example 8

[0060] The preparation of the coumarin chain extender is the same as in Example 1.

[0061] 6.94 g of isophorone diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. 2.7 g of polylactic acid and 0.0347 g of dibutyltin dilaurate were then added, and the mixture was stirred at 75 °C for 2 h to obtain a viscous and transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. Nano-calcium carbonate (2.38 g) mixed with 20 ml of N,N-dimethylformamide and γ-mercaptopropyltriethoxysilane (0.2 g) were simultaneously added to the reaction system, and the mixture was stirred at 40 °C for 2 h to obtain a bio-based photosensitive detachable adhesive.

[0062] The peel strength was measured to be 19.76 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.64 N / 25 mm; the tensile strength was 10.86 MPa, and the elongation at break was 251%; the residual adhesive rate was measured to be 1 / 1278 by microscopic testing.

[0063] Example 9

[0064] The preparation of the coumarin chain extender is the same as in Example 1.

[0065] 5.50 g of isophorone diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. 4.39 g of polytetrahydrofuran glycol and 0.0275 g of dibutyltin dilaurate were then added, and the mixture was stirred at 75 °C for 2 h to obtain a viscous and transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. 1.65 g of nano-calcium carbonate mixed with 20 ml of N,N-dimethylformamide and 0.2 g of γ-mercaptopropyltriethoxysilane were added to the reaction system simultaneously, and the mixture was stirred at 40 °C for 2 h to obtain a bio-based photo-controlled detachable adhesive.

[0066] The peel strength was measured to be 19.26 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.74 N / 25 mm; the tensile strength was 10.34 MPa, and the elongation at break was 249%; the residual adhesive rate was measured to be 1 / 1249 by microscopic testing.

[0067] Example 10

[0068] The preparation of the coumarin chain extender is the same as in Example 1.

[0069] 8g of diphenylmethane diisocyanate dissolved in 20ml of N,N-dimethylformamide was added to a 100ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. 4.39g of polytetrahydrofuran glycol and 0.04g of dibutyltin dilaurate were then added, and the mixture was stirred at 75℃ for 2h to obtain a viscous and transparent prepolymer MU-1. 10.99g of coumarin chain extender dissolved in 20ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36℃ for 1h to obtain a viscous prepolymer MU-2. 2.4g of nano-calcium carbonate mixed with 20ml of N,N-dimethylformamide and 0.2g of γ-mercaptopropyltriethoxysilane were added to the reaction system, and the mixture was stirred at 40℃ for 2h to obtain a bio-based photo-controlled detachable adhesive.

[0070] The peel strength was measured to be 19.15 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.69 N / 25 mm; the tensile strength was 10.27 MPa, and the elongation at break was 246%; the residual adhesive rate was measured to be 1 / 1301 by microscopic testing.

[0071] Example 11

[0072] The preparation of the coumarin chain extender is the same as in Example 1.

[0073] 8.19 g of dicyclohexylmethane diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. 4.39 g of polytetrahydrofuran glycol and 0.041 g of dibutyltin dilaurate were then added, and the mixture was stirred at 75 °C for 2 h to obtain a viscous and transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. 2.46 g of nano-calcium carbonate mixed with 20 ml of N,N-dimethylformamide and 0.2 g of γ-mercaptopropyltrimethoxysilane were added to the reaction system simultaneously, and the mixture was stirred at 40 °C for 2 h to obtain a bio-based photo-controlled detachable adhesive.

[0074] The peel strength was measured to be 18.97 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.68 N / 25 mm; the tensile strength was 10.04 MPa, and the elongation at break was 257%; the residual adhesive rate was measured to be 1 / 1294 by microscopic testing.

[0075] Example 12

[0076] The preparation of the coumarin chain extender is the same as in Example 1.

[0077] 5.25 g of hexamethylene diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. 4.39 g of polytetrahydrofuran glycol and 0.026 g of dibutyltin dilaurate were then added, and the mixture was stirred at 75 °C for 2 h to obtain a viscous and transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. 1.58 g of nano-calcium carbonate mixed with 20 ml of N,N-dimethylformamide and 0.2 g of γ-mercaptopropyltrimethoxysilane were added to the reaction system simultaneously, and the mixture was stirred at 40 °C for 2 h to obtain a bio-based photosensitive detachable adhesive.

[0078] The peel strength was measured to be 19.04 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.71 N / 25 mm; the tensile strength was 9.94 MPa, and the elongation at break was 261%; the residual adhesive rate was measured to be 1 / 1334 by microscopic testing.

[0079] Example 13

[0080] The preparation of the coumarin chain extender is the same as in Example 1.

[0081] 6.94 g of 2,4-toluene diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. Then, 4.39 g of polytetrahydrofuran glycol and 0.0347 g of dibutyltin dilaurate were added, and the mixture was reacted at 75 °C with stirring for 2 h to obtain a viscous, transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. After mixing the silane coupling agent with the organic solvent N,N-dimethylformamide to form a mixed system, nano-calcium carbonate was added, and 20 ml of... 2.08 g of N,N-dimethylformamide mixed silica and 0.2 g of γ-mercaptopropyltrimethoxysilane were added to the reaction system simultaneously and stirred at 40 °C for 2 h to obtain a bio-based light-controlled detachable adhesive.

[0082] The peel strength was measured to be 18.91 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.65 N / 25 mm. The prepared product was tested according to ASTM D882, with a test speed of 500 mm / min. The tensile strength was 10.01 MPa and the elongation at break was 271%. The residual adhesive rate was measured to be 1 / 1349 by microscopic testing.

[0083] Example 14

[0084] The preparation of the coumarin chain extender is the same as in Example 1.

[0085] 6.94 g of 2,4-toluene diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. Then, 4.39 g of polytetrahydrofuran glycol and 0.0347 g of dibutyltin dilaurate were added, and the mixture was reacted at 75 °C with stirring for 2 h to obtain a viscous, transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. After mixing the silane coupling agent with the organic solvent N,N-dimethylformamide to form a mixed system, nano-calcium carbonate was added, and 20 ml of... 2.08 g of carbon black mixed with N,N-dimethylformamide and 0.2 g of γ-(2,3-epoxypropoxy)propyltrimethoxysilane were simultaneously added to the reaction system and stirred at 40 °C for 2 h to obtain a bio-based light-controlled detachable adhesive.

[0086] The peel strength was measured to be 14.91 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.3 N / 25 mm. The prepared product was tested according to ASTM D882, with a test speed of 500 mm / min. The tensile strength was 10.12 MPa and the elongation at break was 278%. The residual adhesive rate was measured to be 1 / 1353 by microscopic testing.

[0087] Example 15

[0088] The preparation of the coumarin chain extender is the same as in Example 1.

[0089] 6.94 g of 2,4-toluene diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. Then, 4.39 g of polytetrahydrofuran glycol and 0.0347 g of dibutyltin dilaurate were added, and the mixture was reacted at 75 °C with stirring for 2 h to obtain a viscous, transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. After mixing the silane coupling agent with the organic solvent N,N-dimethylformamide to form a mixed system, nano-calcium carbonate was added, and 20 ml of... 2.08 g of nano-calcium carbonate mixed with N,N-dimethylformamide and 0.2 g of γ-(2,3-epoxypropoxy)propyltrimethoxysilane were simultaneously added to the reaction system and stirred at 40 °C for 2 h to obtain a bio-based light-controlled detachable adhesive.

[0090] The peel strength was measured to be 17.02 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.59 N / 25 mm. The prepared product was tested according to ASTM D882, with a test speed of 500 mm / min. The tensile strength was 10.04 MPa and the elongation at break was 271%. The residual adhesive rate was measured to be 1 / 1389 by microscopic testing.

[0091] Compare with Example 1

[0092] 5.25 g of hexamethylene diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. 4.39 g of polytetrahydrofuran glycol and 0.026 g of dibutyltin dilaurate were then added, and the mixture was stirred at 75 °C for 2 h to obtain a viscous and transparent prepolymer MU-1. 10.99 g of 4-methylumbelliferone dissolved in 20 ml of N,N-dimethylformamide was added, and a chain extension reaction was carried out at 36 °C for 1 h to obtain a viscous prepolymer MU-2. 1.58 g of nano-calcium carbonate mixed with 20 ml of N,N-dimethylformamide and 0.2 g of γ-(2,3-epoxypropoxy)propyltrimethoxysilane were simultaneously added to the reaction system, and the mixture was stirred at 40 °C for 2 h to obtain a bio-based, light-controlled, detachable, non-stick adhesive.

[0093] The peel strength was measured to be 16.97 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.80 N / 25 mm; the tensile strength was 8.14 MPa, and the elongation at break was 234%; the residual adhesive rate was measured to be 1 / 1050 by microscopic testing.

[0094] Compare with Example 2

[0095] The preparation of the coumarin chain extender is the same as in Example 1.

[0096] 5.25 g of hexamethylene diisocyanate dissolved in 20 ml of N,N-dimethylformamide was added to a 100 ml three-necked flask that had been dried in a forced-air oven and treated with nitrogen. Then, 4.39 g of polytetrahydrofuran glycol and 0.026 g of dibutyltin dilaurate were added, and the mixture was stirred at 75 °C for 2 h to obtain a viscous and transparent prepolymer MU-1. 10.99 g of coumarin chain extender dissolved in 20 ml of N,N-dimethylformamide was added, and the chain extension reaction was carried out at 36 °C for 1 h to obtain a bio-based photosensitive detachable adhesive.

[0097] The peel strength was measured to be 14.95 N / 25 mm, and the peel strength after 15 min of 254 nm UV irradiation was 0.92 N / 25 mm; the tensile strength was 7.58 MPa, and the elongation at break was 259%; the residual adhesive rate was measured to be 1 / 1231 by microscopic testing.

Claims

1. A method for preparing a bio-based, light-controlled, detachable, non-adhesive adhesive, characterized in that: The preparation method steps are as follows: (1) Coumarin chain extender was prepared by irradiating 7-hydroxycoumarin or 4-methylumbelliferone with UV light for 3 hours; (2) Add isocyanate to a nitrogen-filled three-necked flask and dissolve it with an organic solvent. Then add polyol and organotin catalyst and stir at 60-80℃ for 2 hours to obtain a viscous and transparent prepolymer MU-1. (3) Add coumarin chain extender soluble in organic solvent to the prepolymer, and carry out chain extension reaction at 30-40℃ for 1h to obtain prepolymer MU-2; (4) Add the reinforcing material to the organic solvent and stir thoroughly to disperse it. Then add it to MU-2 along with the silane coupling agent. Stir the system at 30-40℃ for 2 hours to obtain the bio-based light-controlled detachable adhesive.

2. The preparation method of the bio-based photosensitive detachable anti-adhesive adhesive as described in claim 1, characterized in that: The isocyanate in step (2) is one of isophorone diisocyanate, 2,4-toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.

3. The preparation method of the bio-based photosensitive detachable anti-adhesive adhesive as described in claim 1, characterized in that: The polyol mentioned in step (2) is one of polytetrahydrofuran diol, polyethylene adipate, polybutylene adipate, polycaprolactone diol, polytetrahydrofuran ether diol, polypropylene glycol, polyethylene glycol, and polylactic acid; the organotin catalyst is dibutyltin dilaurate or stannous octoate.

4. The preparation method of the bio-based photosensitive detachable anti-adhesive adhesive as described in claim 1, characterized in that: In step (2), the molar ratio of isocyanate to polyol is 1.04:1, and the amount of organotin catalyst added is 0.5% of the mass of isocyanate.

5. The preparation method of the bio-based photosensitive detachable anti-adhesive adhesive as described in claim 1, characterized in that: The molar ratio of coumarin chain extender and isocyanate in step (3) is 2:

1.

6. The preparation method of the bio-based photosensitive detachable anti-adhesive adhesive as described in claim 1, characterized in that: The reinforcing material mentioned in step (4) is one of nano-calcium carbonate, silicon dioxide, carbon black, or short fiber, and its addition amount is 0.3-2 times the mass of isocyanate.

7. The preparation method of the bio-based photosensitive detachable anti-adhesive adhesive as described in claim 1, characterized in that: The silane coupling agent in step (4) is one or more of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, vinyltris(b-methoxyethoxy)silane, and 3-aminopropyltrimethoxysilane, and its addition amount is 1% of the mass of the polyol.

8. The method for preparing the bio-based photosensitive detachable anti-adhesive adhesive as described in claim 1, characterized in that: The organic solvents used in steps (2) to (4) are one of N,N-dimethylformamide, acetone, ethyl acetate, butyl acetate, toluene, xylene, dichloromethane, and tetrahydrofuran.

9. An application of a bio-based, light-controlled, detachable, non-stick adhesive prepared by the method according to any one of claims 1-8, characterized in that: The bio-based light-controlled detachable adhesive is used in integrated circuits, optical microscopes, wafer fabrication, and chip manufacturing.

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