High-viscosity high-stripping-degree acrylonitrile resin as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of adhesives, and particularly relates to high-viscosity and high-stripping-degree acrylonitrile resin as well as a preparation method and application thereof. The high-viscosity and high-stripping-degree acrylonitrile resin is prepared by initiating polymerization of a polymeric monomer in an organic solvent through an initiator, the polymeric monomer is prepared from the following raw materials in percentage by mass: 50 to 80 percent of acrylonitrile, 15 to 45 percent of (methyl) acrylate monomer and 1 to 15 percent of allyl diethylene glycol dicarbonate. The acrylonitrile resin provided by the invention has relatively high viscosity and stripping degree, and also has good stability in high-temperature and high-humidity environments.

Description

Technical Field

[0001] The present invention belongs to the technical field of adhesives, and particularly relates to a high-viscosity and high-peel-strength acrylonitrile resin, a preparation method thereof, and an application thereof. Background Art

[0002] Due to its good adhesion, heat resistance, chemical resistance and other properties, acrylonitrile resin has received increasing attention in the field of adhesives in recent years and is widely used in industries such as automotive, construction, and electronics.

[0003] However, the existing acrylonitrile resins have the following disadvantages: (1) They exhibit a relatively low viscosity under certain conditions. A low viscosity leads to excessive fluidity, making it difficult for the adhesive to maintain its shape after coating, resulting in phenomena such as running or dripping, which affects the use effect; the thickness of the bonding layer formed during the curing process is insufficient, affecting the final bonding strength; they contain a relatively high content of volatile components, which may cause the generation of bubbles during the curing process, affecting the transparency and appearance of the adhesive; and they may require a longer time during the curing process, affecting production efficiency. (2) Acrylonitrile resin may exhibit a relatively low peel strength in some formulations, especially when combined with different substrates. Insufficient peel strength causes the adhesive to be unable to withstand external stresses in practical applications, leading to bonding failure and affecting the reliability and safety of the product. (3) Under high-temperature, humid or long-term ultraviolet irradiation environments, acrylonitrile resin will degrade, resulting in a decrease in bonding strength, thus affecting the peel strength. The above problems seriously affect the application of acrylonitrile resin in high-viscosity adhesives.

[0004] Currently, the main directions for modifying acrylonitrile focus on introducing different functional groups or comonomers, as well as adding additives. For example, Chinese Patent No. CN118956302A discloses a modified polyacrylonitrile copolymer adhesive. By weight, the preparation raw materials include 40-60 parts of acrylonitrile, 30-45 parts of flexible (meth)acrylate monomers, 10-30 parts of functional reaction monomers, 0.2-0.5 parts of surfactant, and 0.1-0.15 parts of initiator. The weight of acrylonitrile is not less than 40% of the total mass of acrylonitrile, flexible acrylate monomers, and functional reaction monomers. This technical solution can prepare an adhesive with good adhesion and high softness and has good prospects in the application of battery cathodes. However, the adhesion of the modified polyacrylonitrile copolymer prepared by this technical solution can only reach 8.3 N / m, and the peel strength needs to be improved. In addition, this technical solution is an aqueous polyacrylonitrile copolymer, and its peel force may decrease under high-temperature and high-humidity environments.

[0005] Chinese Patent No. CN 117264115 A discloses a soap-free emulsion binder, a negative electrode of a lithium-ion battery, and a lithium-ion battery. The binder is obtained by soap-free emulsion polymerization of polymerization monomers. By weight percentage, the polymerization monomers include: 40-85% acrylonitrile, 10-40% acrylic acid monomers, 5-25% acrylamide monomers, 0-5% acrylate monomers, and 0.1-5% crosslinking agent. The binder of this technical solution uses acrylonitrile as the backbone, introduces an appropriate amount of acrylic acid monomers and strongly polar acrylamide monomers, and is prepared by a polymerization reaction with the simultaneous addition of a crosslinking agent. The binder has more excellent peel strength. When used on the negative electrode of a lithium battery, the amount of the binder used is reduced, the internal resistance of the battery is lower, and the energy density and rate performance of the lithium-ion battery can be improved. However, this technical solution is also an aqueous acrylonitrile copolymer, which will affect its peel force under high temperature and high humidity conditions. Summary of the Invention

[0006] In view of the above problems, the present invention provides a high-viscosity and high-peel acrylonitrile resin, its preparation method and application. By introducing (meth)acrylate and allyl diglycol dicarbonate into the polyacrylonitrile chain, the viscosity and peel strength of the acrylonitrile resin are improved. At the same time, its mechanical strength and heat resistance are also improved, its stability in high temperature and high humidity environments is enhanced, and its application performance in adhesives is improved.

[0007] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] In the first aspect of the present invention, a high-viscosity and high-peel acrylonitrile resin is provided. The high-viscosity and high-peel acrylonitrile resin is polymerized from polymerization monomers in an organic solvent under the initiation of an initiator. By mass percentage, the raw materials of the polymerization monomers include 50-80% acrylonitrile, 15-45% (meth)acrylate monomers, and 1-15% allyl diglycol dicarbonate.

[0009] In some preferred embodiments, the (meth)acrylate monomers are selected from one or more combinations of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, isobornyl acrylate, amyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, lauryl acrylate, lauryl methacrylate, and isodecyl acrylate.

[0010] Preferably, the (meth)acrylate monomers are at least one of isooctyl acrylate and butyl acrylate, and more preferably isooctyl acrylate.

[0011] Through the above technical solution, (meth)acrylate and allyl diglycol dicarbonate are introduced onto the polyacrylonitrile chain. (Meth)acrylate reduces the rigidity of the polyacrylonitrile main chain and provides the entanglement ability between molecular chains. The allyl diglycol dicarbonate contains bis-carbonate groups and allyl double bonds, which can form a dual cross-linked network through free radical initiation, and then form an acrylonitrile resin with a three-dimensional network structure. The three-dimensional network structure improves the cohesive strength of the acrylonitrile resin, and at the same time restricts the slippage, thermal movement and water molecule penetration of the molecular chain, thereby improving the viscosity, peel strength and high temperature and high humidity resistance of the acrylonitrile resin.

[0012] In some preferred embodiments, the mass percentages of acrylonitrile that can be enumerated are 50%, 55%, 58%, 60%, 63%, 67%, 70%, 75%, 77%, 80%.

[0013] In some preferred embodiments, the mass percentages of the (meth)acrylate monomer that can be enumerated are 5%, 20%, 22%, 25%, 28%, 30%, 35%, 38%, 40%, 45%.

[0014] In some preferred embodiments, the mass percentages of allyl diglycol dicarbonate that can be enumerated are 1%, 2%, 4%, 5%, 7%, 8%, 10%, 12%, 13%, 15%.

[0015] In some preferred embodiments, for the polymerization monomer, by mass percentage, the raw materials include 60 - 70% of acrylonitrile, 25 - 38% of (meth)acrylate monomer, and 2 - 4% of allyl diglycol dicarbonate.

[0016] Preferably, for the polymerization monomer, by mass percentage, the raw materials include 70% of acrylonitrile, 25 - 27% of (meth)acrylate monomer, and 3 - 4% of allyl diglycol dicarbonate.

[0017] Most preferably, for the polymerization monomer, by mass percentage, the raw materials include 70% of acrylonitrile, 27% of (meth)acrylate monomer, and 3% of allyl diglycol dicarbonate.

[0018] Through the above technical solution, by controlling the ratios of acrylonitrile, (meth)acrylate and allyl diglycol dicarbonate, the decrease in the peel strength and high temperature and high humidity resistance of the acrylonitrile resin is avoided.

[0019] In some other preferred embodiments, allyl diglycol dicarbonate is replaced with pentamethylphenyl dihydrotrisiloxane modified allyl diglycol dicarbonate.

[0020] Preferably, the preparation method of the pentamethylphenyl dihydro trisiloxane modified allyl diglycol dicarbonate is as follows: under nitrogen protection, pentamethylphenyl dihydro trisiloxane and allyl diglycol dicarbonate are subjected to a hydrosilylation reaction under the action of chloroplatinic acid to obtain the product.

[0021] Preferably, the mass ratio of the pentamethylphenyl dihydro trisiloxane to the allyl diglycol dicarbonate is 1:1.1 - 1.2.

[0022] Preferably, the temperature of the hydrosilylation reaction is 60 - 70 °C.

[0023] Preferably, the time of the hydrosilylation reaction is 2 - 4 h.

[0024] Preferably, the dosage of the chloroplatinic acid is 5 - 10 ppm (calculated by the mass of platinum) of the total mass of the pentamethylphenyl dihydro trisiloxane and the allyl diglycol dicarbonate.

[0025] Surprisingly, it is found that replacing the allyl diglycol dicarbonate with the pentamethylphenyl dihydro trisiloxane modified allyl diglycol dicarbonate can not only avoid a significant decrease in the viscosity and peel strength of the acrylonitrile resin, which may be because the structure of the pentamethylphenyl dihydro trisiloxane just compensates for the decrease in viscosity and peel strength caused by the decrease in the crosslinking strength of the acrylonitrile resin; more importantly, replacing the allyl diglycol dicarbonate with the pentamethylphenyl dihydro trisiloxane modified allyl diglycol dicarbonate can significantly improve the electrolyte resistance of the acrylonitrile resin.

[0026] In some preferred embodiments, the organic solvent is selected from one or more combinations of ethyl acetate, dimethyl sulfoxide, chloroform, carbon tetrachloride, tetrahydrofuran, cyclohexane, cyclohexanone, acetone, toluene, xylene, N,N - dimethylformamide, N,N - dimethylacetamide, and N - methylpyrrolidone.

[0027] Preferably, the organic solvent is N,N - dimethylformamide.

[0028] In some preferred embodiments, the dosage of the organic solvent is 60 - 85% of the total mass of the organic solvent and the polymerization monomer, and examples include 60%, 65%, 70%, 75%, 77%, 80%, 82%, 85%.

[0029] In some preferred embodiments, the initiator is selected from one or more combinations of ammonium persulfate, potassium persulfate, benzoyl peroxide, dicumyl peroxide, dibenzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, and azodipentanoic acid.

[0030] Preferably, the initiator is azobisisobutyronitrile.

[0031] In some preferred embodiments, the amount of the initiator is 0.3%-2% of the mass of the polymerization monomer. Examples include 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, and 2%.

[0032] The second aspect of the present invention provides a method for preparing the above-mentioned high-viscosity and high-peel-strength acrylonitrile resin, which includes the following steps: placing the polymerization monomer in an organic solvent and mixing evenly, adding an initiator and mixing evenly, and then carrying out a polymerization reaction to obtain the product.

[0033] In some preferred embodiments, the temperature of the polymerization reaction is 60-80°C, and the time of the polymerization reaction is 6-12 h.

[0034] Preferably, the temperature of the polymerization reaction is 70-80°C. Examples include 70°C, 72°C, 75°C, 77°C, and 80°C.

[0035] Preferably, the time of the polymerization reaction can be 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, or 12 h.

[0036] Preferably, the polymerization reaction process is carried out with stirring under an inert gas, and the inert gas is any one of nitrogen and argon.

[0037] The third aspect of the present invention provides the application of the above-mentioned high-viscosity and high-peel-strength acrylonitrile resin in the preparation of adhesives.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] 1. The present invention creatively introduces (meth)acrylate and allyl diglycol dicarbonate onto the polyacrylonitrile chain to form an acrylonitrile resin with a three-dimensional network structure, improving the viscosity, peel strength, high-temperature and high-humidity resistance of the acrylonitrile resin, and enhancing its application performance in adhesives.

[0040] 2. The present invention controls the ratios of acrylonitrile, (meth)acrylate, and allyl diglycol dicarbonate, avoiding the decrease in the peel strength and high-temperature and high-humidity resistance of the acrylonitrile resin.

[0041] 3. The present invention replaces allyl diglycol dicarbonate with pentamethylphenyl dihydrotrisiloxane-modified allyl diglycol dicarbonate, which can not only avoid a significant decrease in the viscosity and peel strength of the acrylonitrile resin, but also significantly improve the electrolyte resistance of the acrylonitrile resin. Specific Embodiments

[0042] In order to have a clearer understanding of the technical features, objectives, and effects of the present invention, the specific implementation manners are described in detail below.

[0043] The present invention will be further described below in conjunction with embodiments, but the present invention is not limited to the following embodiments. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not specified are the conventional conditions in this industry. The technical features involved in various embodiments of the present invention can be combined with each other as long as they do not conflict with each other.

[0044] In the following examples and comparative examples, unless otherwise specified, the raw materials used are all commercially available or prepared by conventional methods in this field.

[0045] N,N-dimethylformamide (CAS No.: 68-12-2); azobisisobutyronitrile (CAS No.: 78-67-1); acrylonitrile (CAS No.: 107-13-1); isooctyl acrylate (CAS No.: 29590-42-9); allyl diglycol carbonate (CAS No.: 142-22-3); diallylamine (CAS No.: 124-02-7); ethylene glycol dimethacrylate (CAS No.: 97-90-5); butyl acrylate (CAS No.: 141-32-2); ethylene glycol methyl ether acrylate (CAS No.: 3121-61-7); acrylamide (CAS No.: 79-06-1); pentamethylphenyl dihydrotrisiloxane (CAS No.: 17962-34-4); styrene (CAS No.: 100-42-5).

[0046] Example 1

[0047] A high-viscosity and high-peel-strength acrylonitrile resin: By mass, 100 parts of polymerization monomers are placed in 285 parts of N,N-dimethylformamide and mixed evenly, 0.4 part of azobisisobutyronitrile is added and stirred evenly, nitrogen is filled for 30 min to remove oxygen, and a polymerization reaction is carried out for 8 h under the conditions of nitrogen, 200 rpm, and 77 °C to obtain.

[0048] The polymerization monomers are composed of 70% acrylonitrile, 28% isooctyl acrylate, and 2% allyl diglycol carbonate by mass percentage.

[0049] Example 2

[0050] The difference from Example 1 is that the polymerization monomers are composed of 70% acrylonitrile, 27% isooctyl acrylate, and 3% allyl diglycol carbonate by mass percentage; the rest are the same.

[0051] Comparative Example 1

[0052] The difference from Example 2 is that allyl diglycol carbonate is replaced with the same mass of isooctyl acrylate, that is, the polymerization monomers are composed of 70% acrylonitrile and 30% isooctyl acrylate by mass percentage; the rest are the same.

[0053] Comparative Example 2

[0054] The difference from Example 2 is that allyl diglycol dicarbonate is replaced with the same mass of diallylamine; the rest are the same.

[0055] Comparative Example 3

[0056] The difference from Example 2 is that allyl diglycol dicarbonate is replaced with the same mass of ethylene glycol dimethacrylate; the rest are the same.

[0057] Comparative Example 4

[0058] The difference from Example 2 is that the polymerization monomer, by mass percentage, consists of 70% acrylonitrile, 10% isooctyl acrylate, and 20% allyl diglycol dicarbonate; the rest are the same.

[0059] Example 3

[0060] The difference from Example 1 is that the polymerization monomer, by mass percentage, consists of 70% acrylonitrile, 25% isooctyl acrylate, and 5% allyl diglycol dicarbonate; the rest are the same.

[0061] Example 4

[0062] The difference from Example 1 is that the polymerization monomer, by mass percentage, consists of 60% acrylonitrile, 38% isooctyl acrylate, and 2% allyl diglycol dicarbonate; the rest are the same.

[0063] Example 5

[0064] The difference from Example 1 is that 0.8 parts of azobisisobutyronitrile are added; the rest are the same.

[0065] Example 6

[0066] The difference from Example 1 is that the polymerization reaction is carried out for 10 h under the conditions of nitrogen, 200 rpm, and 77 °C; the rest are the same.

[0067] Example 7

[0068] The difference from Example 1 is that the polymerization monomer, by mass percentage, consists of 80% acrylonitrile, 18% isooctyl acrylate, and 2% allyl diglycol dicarbonate; the rest are the same.

[0069] Example 8

[0070] The difference from Example 1 is that isooctyl acrylate is replaced with the same mass of butyl acrylate; the rest are the same.

[0071] Comparative Example 5

[0072] An acrylonitrile resin: by mass, (1) in 800 parts of water, after adding 0.2 part of sodium dodecyl sulfate, 40 parts of acrylonitrile, 25 parts of isooctyl acrylate, 5 parts of ethylene glycol methyl ether acrylate, and 10 parts of acrylamide are added. Nitrogen is passed to remove oxygen, and the mixture is stirred and mixed evenly. Then, the temperature of the reaction kettle is raised to 70 °C.

[0073] 0.08 part of ammonium persulfate is added to 40 parts of water and stirred and mixed evenly to obtain an initiator solution. The initiator solution is added dropwise to the liquid in step (1) and added dropwise within 1.5 h. After the addition is completed, the reaction is kept warm for 2.5 h. Then, 0.02 part of ammonium persulfate (dissolved in 10 parts of water) and 20 parts of acrylonitrile are added, the temperature is raised to 75 °C and kept warm for 3 h. Then, 0.02 part of ammonium persulfate is added, and it is kept warm at 75 °C for 1 h to obtain the product.

[0074] Example 9

[0075] The difference from Example 2 is that allyl diglycol dicarbonate is replaced with pentamethylphenyl dihydrotrisiloxane-modified allyl diglycol dicarbonate of the same mass.

[0076] The preparation method of the pentamethylphenyl dihydrotrisiloxane-modified allyl diglycol dicarbonate is as follows: under nitrogen protection, pentamethylphenyl dihydrotrisiloxane and allyl diglycol dicarbonate carry out a hydrosilylation reaction under the action of chloroplatinic acid to obtain the product.

[0077] The mass ratio of the pentamethylphenyl dihydrotrisiloxane to the allyl diglycol dicarbonate is 1:1.1.

[0078] The temperature of the hydrosilylation reaction is 65 °C.

[0079] The time of the hydrosilylation reaction is 3 h.

[0080] The dosage of the chloroplatinic acid is 10 ppm (calculated by the mass of platinum) of the total mass of the pentamethylphenyl dihydrotrisiloxane and the allyl diglycol dicarbonate.

[0081] Comparative Example 6

[0082] The difference from Example 9 is that the pentamethylphenyl dihydrotrisiloxane-modified allyl diglycol dicarbonate is replaced with hydrogen-terminated polydimethylsiloxane-modified allyl diglycol dicarbonate and styrene, that is: the polymerization monomers, by mass percentage, are composed of 70% acrylonitrile, 27% isooctyl acrylate, 2% hydrogen-terminated polydimethylsiloxane-modified allyl diglycol dicarbonate, and 1% styrene;

[0083] The hydrogen content of the hydrogen-terminated polydimethylsiloxane is 0.18 ± 0.1 wt%, purchased from Ningbo Runhe New Materials Technology Co., Ltd., model RH-H518.

[0084] The preparation method of the hydrogen-terminated polydimethylsiloxane-modified allyl diglycol dicarbonate is the same as that of the pentamethylphenyl dihydro trisiloxane-modified allyl diglycol dicarbonate, except that the mass ratio of the hydrogen-terminated polydimethylsiloxane to the allyl diglycol dicarbonate is 3.5:1; the rest are the same.

[0085] Performance testing:

[0086] 1. Viscosity detection: It was measured using a Shanghai Yixin NDJ-1S digital viscometer at a temperature of 25 °C.

[0087] 2. Peel strength: By weight, 95 parts of lithium manganate, 3 parts of acetylene black, and 2 parts of the prepared acrylonitrile resin were mixed evenly with 100 parts of NMP (N-methylpyrrolidone) using a stirrer, and the slurry was coated on aluminum foil (thickness 18 μm) using a coater, with a coating areal density of 2 g / cm 2 ; After baking and rolling, it was compacted to 2.85 g / cm 3 to obtain a pole piece. The pole piece was tested using an electronic tensile testing machine. Referring to the national standard GB / T 2792-2014 "Test Method for Peel Strength of Adhesive Tapes", a 180° peel test method was used, and the peel force was tested at a tensile speed of 5 mm / min.

[0088] 3. High temperature and high humidity resistance: By weight, 95 parts of lithium manganate, 3 parts of acetylene black, and 2 parts of the prepared acrylonitrile resin were mixed evenly with 100 parts of NMP using a stirrer, and the slurry was coated on aluminum foil (thickness 18 μm) using a coater, with a coating areal density of 2 g / cm 2 ; After baking and rolling, it was compacted to 2.85 g / cm 3 to obtain a pole piece. The pole piece was placed in a constant temperature and humidity chamber at 85 °C and 85% RH for 168 h, taken out and placed in a constant temperature room at 25 °C for 24 h, and then tested using an electronic tensile testing machine. Referring to the national standard GB / T 2792-2014 "Test Method for Peel Strength of Adhesive Tapes", a 180° peel test method was used, and the peel force was tested at a tensile speed of 5 mm / min.

[0089] 4. Electrolyte resistance: By weight, 95 parts of lithium manganate, 3 parts of acetylene black, and 2 parts of the prepared acrylonitrile resin were mixed evenly with 100 parts of NMP using a stirrer, and the slurry was coated on aluminum foil (thickness 18 μm) using a coater, with a coating areal density of 2 g / cm 2 ; After baking and rolling, it was compacted to 2.85 g / cm 3After obtaining the electrode sheet, the electrode sheet is immersed in an electrolyte (composition: ethylene carbonate, diethyl carbonate, dimethyl carbonate, and lithium hexafluorophosphate; the molar amounts of ethylene carbonate, diethyl carbonate, and dimethyl carbonate are 1:1:1; the molar amount of lithium hexafluorophosphate is 1.0 mol / L) for 48 h. After taking it out, the residue is washed off with clean water. After drying, it is tested with an electronic tensile testing machine. Referring to the national standard GB / T 2792-2014 "Test Method for Peel Strength of Adhesive Tape", the 180° peel test method is adopted, and the peel force is tested at a tensile speed of 5 mm / min.

[0090] Table 1 Performance test results of high-viscosity and high-peel acrylonitrile resins in Examples 1-8

[0091]

[0092]

[0093] It can be seen from Table 1 that: the viscosities and peel forces of the acrylonitrile resins in Examples 1-8 are both high; the change in peel strength after the high-temperature and high-humidity test is small;

[0094] Comparing Examples 1-3, as the content of allyl diglycol dicarbonate increases, the viscosity and peel strength of the acrylonitrile resin increase, indicating that the addition of allyl diglycol dicarbonate reacts with isooctyl acrylate to form a three-dimensional network structure by crosslinking, improving the viscosity and peel strength of the acrylonitrile resin. Among them, the effect of Example 2 is the best, and they all have good high-temperature and high-humidity resistance;

[0095] Comparing Example 1 with Example 4, reducing the content of acrylonitrile and increasing the amount of isooctyl acrylate will cause the viscosity and peel strength of the acrylonitrile resin to decrease. It is speculated that this may be because the reduction in the content of acrylonitrile leads to a decrease in the polar functional groups in the molecule, a weakening of the intermolecular cohesion, a decrease in viscosity and peel force, and a slight decrease in high-temperature and high-humidity resistance.

[0096] Comparing Example 1 with Example 5, the dosage of the initiator will also affect the viscosity and peel strength of the acrylonitrile resin. Increasing the dosage of the initiator within a certain range can improve the viscosity and peel strength of the acrylonitrile resin.

[0097] Comparing Example 1 with Example 6, the reaction time will also affect the viscosity and peel strength of the acrylonitrile resin. Extending the reaction time within a certain range can also improve the viscosity and peel strength of the acrylonitrile resin.

[0098] Comparing Example 1 with Example 7, increasing the amount of acrylonitrile slightly increases the peel strength but decreases the viscosity.

[0099] Comparing Example 1 with Example 8, replacing other (meth)acrylate monomers can also obtain similar acrylonitrile resins.

[0100] Table 2 Performance test results of high-viscosity and high-peeling-strength acrylonitrile resins of Comparative Examples 1-5

[0101]

[0102]

[0103] It can be seen from Table 2 that: when comparing Comparative Example 1 with Example 2, the viscosity, peeling strength, and high-temperature and high-humidity resistance of the acrylonitrile resin without allyl diglycol dicarbonate decreased significantly;

[0104] When comparing Comparative Example 2 with Example 2, after replacing allyl diglycol dicarbonate with diallylamine, the viscosity, peeling strength, and high-temperature and high-humidity resistance of the acrylonitrile resin decreased significantly;

[0105] When comparing Comparative Example 3 with Example 2, after replacing allyl diglycol dicarbonate with ethylene glycol dimethacrylate, the viscosity, peeling strength, and high-temperature and high-humidity resistance of the acrylonitrile resin also decreased;

[0106] When comparing Comparative Example 4 with Example 2, by increasing the amount of allyl diglycol dicarbonate, the acrylonitrile resin had a high viscosity, was slightly gelled, had a low peeling strength, and the high-temperature and high-humidity resistance decreased;

[0107] When comparing Comparative Example 5 with Example 2, the viscosity and peeling strength of the emulsion-type acrylonitrile resin decreased, and the high-temperature and high-humidity resistance decreased significantly.

[0108] Table 3 Performance test results of high-viscosity and high-peeling-strength acrylonitrile resins of Example 2, Example 9 and Comparative Example 6

[0109]

[0110] It can be seen from Table 3 that in Example 9, when replacing allyl diglycol dicarbonate with pentamethylphenyl dihydrotrisiloxane-modified allyl diglycol dicarbonate of the same mass, not only will the peeling strength of the acrylonitrile resin not be significantly reduced, but the obtained acrylonitrile resin not only has a high viscosity, high-temperature and high-humidity resistance, but also electrolyte resistance;

[0111] When comparing Comparative Example 6 with Example 2, when replacing allyl diglycol dicarbonate with pentamethylphenyl dihydrotrisiloxane-modified allyl diglycol dicarbonate of the same mass, although the viscosity and electrolyte resistance increased slightly, the peeling strength was low. It is speculated that due to the increased flexibility of the polydimethylsiloxane chain segment, the mobility of the acrylonitrile resin molecular chain increased, resulting in a decrease in its viscosity and peeling strength.

[0112] Comparative Example 6 is compared with Example 9. Even if pentamethylphenyldihydrotrisiloxane-modified allyl diglycol dicarbonate is replaced with hydride-terminated polydimethylsiloxane-modified allyl diglycol dicarbonate and styrene, although both siloxane and phenyl group exist in the obtained acrylonitrile resin, its peel strength and electrolyte resistance performance are not good.

[0113] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than limiting the protection scope of the present invention. Any simple modification or equivalent replacement made by those of ordinary skill in the art to the technical solution of the present invention does not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A high-viscosity and high-peelability acrylonitrile resin, characterized in that: The high-viscosity and high-peelability acrylonitrile resin is prepared by polymerization of monomers in an organic solvent initiated by an initiator; the monomers, by mass percentage, include 50-80% acrylonitrile, 15-45% (methyl) acrylic acid ester monomers and 1-15% allyl diglycol dicarbonate.

2. The high-viscosity and high-peelability acrylonitrile resin according to claim 1, characterized in that: The (meth)acrylate monomer is selected from one or more combinations of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, isobornyl acrylate, amyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, lauryl acrylate, lauryl methacrylate and isodecyl acrylate.

3. The high-viscosity and high-peelability acrylonitrile resin according to claim 2, characterized in that: The (meth)acrylate monomer is at least one of isooctyl acrylate and butyl acrylate.

4. The high-viscosity and high-peelability acrylonitrile resin according to claim 1, characterized in that: The polymerizable monomers include, by mass percentage, 60-70% acrylonitrile, 26-38% (meth)acrylate monomers and 2-4% allyl diglycol dicarbonate.

5. The high-viscosity and high-peelability acrylonitrile resin according to claim 4, characterized in that: The polymerizable monomers include, by mass percentage, 70% acrylonitrile, 26-27% (meth)acrylate monomers and 3-4% allyl diglycol dicarbonate.

6. The high-viscosity and high-peelability acrylonitrile resin according to claim 5, characterized in that: The polymerizable monomers include, by mass percentage, 70% acrylonitrile, 27% (meth)acrylate monomers and 3% allyl diglycol dicarbonate.

7. The high-viscosity and high-peelability acrylonitrile resin according to claim 6, characterized in that: Allyl diglycol dicarbonate was replaced with pentamethylphenyl dihydrogen trisiloxane-modified allyl diglycol dicarbonate.

8. The method for preparing a high-viscosity and high-peelability acrylonitrile resin according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: placing polymerization monomers in an organic solvent, mixing, stirring evenly, adding an initiator, stirring evenly, and performing polymerization reaction to obtain the product.

9. The method for preparing a high-viscosity and high-peelability acrylonitrile resin according to claim 8, characterized in that: The polymerization reaction temperature is 60-80° C., and the polymerization reaction time is 6-12 hours.

10. Use of the high-viscosity and high-peelability acrylonitrile resin obtained by the method for preparing the high-viscosity and high-peelability acrylonitrile resin according to any one of claims 1 to 7 or the high-viscosity and high-peelability acrylonitrile resin according to any one of claims 8 to 9 in preparing an adhesive.

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