阅读说明：本技术 一种高耐热单组份胶黏剂及其制备方法 (High-heat-resistance single-component adhesive and preparation method thereof ) 是由 易强 宋贤锋 陈立兴 周友 于 2021-09-06 设计创作，主要内容包括：本发明公开了一种高耐热单组份胶黏剂及其制备方法,其特征是：高耐热单组份胶黏剂由增韧改性双马来酰亚胺树脂5～30重量份、环氧树脂15～55重量份、环氧活性稀释剂0.1～5重量份、潜伏型固化剂3～18重量份、消泡剂0.01～0.5重量份、润湿分散剂0.01～0.5重量份、催化剂0.1～5重量份和无机填料5～60重量份混合组成。制备方法是先制备双马来酰亚胺树脂并经增韧改性处理,再与其它原料加入真空行星搅拌机混合即得。本发明高耐热单组份胶黏剂具有固化过程放热平缓、固化物高耐热性、高韧性、低热膨胀系数、耐高低温冲击能力好等特点,适用于有耐热及环境温度要求的电子电器元件、金属和非金属器件的粘接及密封。(The invention discloses a high-heat-resistance single-component adhesive and a preparation method thereof, and is characterized in that: the high-heat-resistance single-component adhesive is prepared by mixing 5-30 parts by weight of toughened modified bismaleimide resin, 15-55 parts by weight of epoxy resin, 0.1-5 parts by weight of epoxy active diluent, 3-18 parts by weight of latent curing agent, 0.01-0.5 part by weight of defoaming agent, 0.01-0.5 part by weight of wetting dispersant, 0.1-5 parts by weight of catalyst and 5-60 parts by weight of inorganic filler. The preparation method comprises the steps of firstly preparing the bismaleimide resin, toughening and modifying the bismaleimide resin, and then adding the bismaleimide resin and other raw materials into a vacuum planetary mixer for mixing. The high heat-resistant single-component adhesive has the characteristics of mild heat release in the curing process, high heat resistance of a cured product, high toughness, low thermal expansion coefficient, good high and low temperature impact resistance and the like, and is suitable for bonding and sealing electronic and electric elements, metal and nonmetal devices with heat resistance and environmental temperature requirements.)

1. The high-heat-resistance single-component adhesive is characterized by comprising the following components in parts by weight: the composite material is prepared by mixing 5-30 parts by weight of toughened modified bismaleimide resin, 15-55 parts by weight of epoxy resin, 0.1-5 parts by weight of epoxy active diluent, 3-18 parts by weight of latent curing agent, 0.01-0.5 part by weight of defoaming agent, 0.01-0.5 part by weight of wetting dispersant, 0.1-5 parts by weight of catalyst and 5-60 parts by weight of inorganic filler.

2. The high heat-resistant single-component adhesive as claimed in claim 1, which is characterized in that: the toughened and modified bismaleimide resin is a prepolymerization product of bismaleimide resin and an allyl compound; the bismaleimide resin has a chemical structural formula shown in a formula (I), and the allyl compound is a monoallyl compound or a diallyl compound;

in formula (I): r₁And R₂Is C1-C10 alkyl or aryl; n is 1 to 400.

3. The high heat-resistant single-component adhesive as claimed in claim 2, which is characterized in that: the allyl compound is any one of diallyl bisphenol A, diallyl bisphenol S, polyallyl ether ketone resin, allyl phenol epoxy resin, allyl phenol-formaldehyde linear resin, N-allyl arylamine compound and silicon modified allyl compound.

4. The high heat-resistant single-component adhesive as claimed in claim 1, 2 or 3, which is characterized in that: the epoxy resin is one or a mixture of more than two of glycidyl ether type difunctional epoxy resin, glycidyl ether type multifunctional epoxy resin, toughened and modified glycidyl ether type difunctional epoxy resin and toughened and modified glycidyl ether type multifunctional epoxy resin; the glycidyl ether type difunctional epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether and aliphatic glycidyl ether; the glycidyl ether type multifunctional epoxy resin is phenol type novolac epoxy resin, o-cresol type novolac epoxy resin or bisphenol A type novolac epoxy resin; the toughened and modified epoxy resin is rubber toughened epoxy resin, hyperbranched polymer toughened epoxy resin, thermoplastic resin toughened epoxy resin or thermotropic liquid crystal polymer toughened epoxy resin.

5. The high heat-resistant single-component adhesive as claimed in claim 1, 2 or 3, which is characterized in that: the latent curing agent is one or a mixture of more than two of dicyandiamide, imidazoles, aromatic amines, organic hydrazides and organic acid anhydrides;

the epoxy active diluent is one or a mixture of more than two of benzyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, C12-C14 monoglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether and polypropylene glycol diglycidyl ether;

the defoaming agent is one or a mixture of more than two of a non-silicon polymer defoaming agent, an organic silicon polymer compound defoaming agent and a modified organic silicon defoaming agent;

the wetting dispersant has viscosity reduction and anti-settling functions, and a rheological additive can be compounded with the wetting dispersant;

the catalyst is one or a mixture of more than two of imidazoles, organic ureas and peroxides;

the inorganic filler is one or two of spherical silica micropowder and boehmite.

6. A preparation method of a high-heat-resistance single-component adhesive is characterized by comprising the following steps:

a. preparation of bismaleimide resin:

(a) adding 0.1-0.15 mol of maleic anhydride and 200mL of solvent into a reactor provided with a stirrer, a thermometer and a reflux condenser, stirring for dissolving, then adding 0.1-0.15 mol of p-aminophenol, reacting for 2-3 h at room temperature, then adding 0.0001-0.001 mol of catalyst, heating for refluxing for 3-4 h, then cooling, elutriating, filtering, and recrystallizing to obtain N- (4-hydroxyphenyl) maleimide;

(b) adding 0.1mol of N- (4-hydroxyphenyl) maleimide and 100mL of solvent into a reactor A provided with a stirrer, a thermometer and a reflux condenser, and stirring for dissolving; adding 0.05mol of chlorine-terminated polysiloxane, 50mL of solvent and 0.05-0.2 mol of alkaline substance into another container B to prepare a mixed solution C; dripping the mixed solution C into the reactor A through a constant-pressure dropping funnel at the temperature of 0-10 ℃, reacting at room temperature for 4-5 hours after dripping, and then carrying out elutriation, filtration and washing to obtain bismaleimide resin;

the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and acetone;

the catalyst is sodium acetate or nickel acetate;

the alkaline substance is pyridine or triethylamine;

b. toughening modification of bismaleimide resin:

adding 0.1mol of bismaleimide resin into a reactor, heating to 100-140 ℃ to melt the bismaleimide resin, adding 0.01-0.1 mol of allyl compound, stirring at 100-140 ℃ for 10-60 min at constant temperature, discharging, cooling, and grinding into powder to obtain the toughened modified bismaleimide resin;

the allyl compound is a monoallyl compound or a diallyl compound;

c. preparing a high-heat-resistant single-component adhesive:

preparing materials: taking raw materials of 5-30 parts by weight of toughened modified bismaleimide resin, 15-55 parts by weight of epoxy resin, 0.1-5 parts by weight of epoxy active diluent, 3-18 parts by weight of latent curing agent, 0.01-0.5 part by weight of defoaming agent, 0.01-0.5 part by weight of wetting dispersant, 0.1-5 parts by weight of catalyst and 5-60 parts by weight of inorganic filler;

mixing: firstly, adding epoxy resin, toughened modified bismaleimide resin, an epoxy active diluent, a defoaming agent and a wetting dispersant into a vacuum planetary stirring kettle, starting stirring and mixing uniformly, adding an inorganic filler, mixing uniformly again, adding a latent curing agent and a catalyst when the temperature of materials in the stirring kettle is reduced to normal temperature, starting stirring and vacuum to uniformly mix the materials and remove air in the materials, and thus obtaining the high-heat-resistant single-component adhesive.

7. The preparation method of the high-heat-resistance single-component adhesive as claimed in claim 6 is characterized in that: in the step b, the allyl compound is any one of diallyl bisphenol A, diallyl bisphenol S, polyallyl ether ketone resin, allyl phenol epoxy resin, allyl phenol novolac resin, N-allyl arylamine compound and silicon modified allyl compound.

8. The high heat-resistant one-component adhesive as claimed in claim 6 or 7, which is characterized in that: the epoxy resin is one or a mixture of more than two of glycidyl ether type difunctional epoxy resin, glycidyl ether type multifunctional epoxy resin, toughened and modified glycidyl ether type difunctional epoxy resin and toughened and modified glycidyl ether type multifunctional epoxy resin; the glycidyl ether type difunctional epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether and aliphatic glycidyl ether; the glycidyl ether type multifunctional epoxy resin is phenol type novolac epoxy resin, o-cresol type novolac epoxy resin or bisphenol A type novolac epoxy resin; the toughened and modified epoxy resin is rubber toughened epoxy resin, hyperbranched polymer toughened epoxy resin, thermoplastic resin toughened epoxy resin or thermotropic liquid crystal polymer toughened epoxy resin.

9. The high heat-resistant one-component adhesive as claimed in claim 6 or 7, which is characterized in that: the latent curing agent is one or a mixture of more than two of dicyandiamide, imidazole, aromatic amine, organic hydrazide and organic anhydride.

10. The high heat-resistant one-component adhesive as claimed in claim 6 or 7, which is characterized in that: the epoxy active diluent is one or a mixture of more than two of benzyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, C12-C14 monoglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether and polypropylene glycol diglycidyl ether;

the defoaming agent is one or a mixture of more than two of a non-silicon polymer defoaming agent, an organic silicon polymer compound defoaming agent and a modified organic silicon defoaming agent;

the wetting dispersant has the functions of viscosity reduction and anti-settling, or is compounded by using a rheological additive and the wetting dispersant;

the catalyst is one or a mixture of more than two of imidazoles, organic ureas and peroxides;

the inorganic filler is one or two of spherical silica micropowder and boehmite.

Technical Field

The invention belongs to an adhesive and preparation thereof, and relates to a high-heat-resistance single-component adhesive and a preparation method thereof. The high heat-resistant single-component adhesive is suitable for bonding of metal, nonmetal, thermosetting polymer materials and the like, and is particularly suitable for bonding and sealing of electronic and electric elements, metal and nonmetal devices with heat resistance and environmental temperature requirements.

Background

The epoxy resin adhesive has good adhesive property to metal, nonmetal, thermosetting polymer materials and the like, has strong adaptability, is green and environment-friendly, plays an important role in the adhesive industry, and is widely applied to the industries of mechanical manufacturing, electronics, buildings, aerospace and the like. Compared with a two-component epoxy resin adhesive, the single-component epoxy resin adhesive has the advantages of convenience in operation, long service cycle and the like, and has an irreplaceable position in an application scene without field metering and mixing.

Like the two-component epoxy adhesive, the one-component epoxy adhesive has the problems of insufficient heat resistance, high brittleness and the like, and is limited to be applied in the field of high heat resistance and high reliability. Meanwhile, the curing time of the single-component epoxy adhesive is shorter, the residual stress is larger, and the cracking problem is easier to occur. Although various epoxy modification methods are widely researched, the improvement effect is not obvious, and the single-component epoxy resin adhesive still has the problems of insufficient heat resistance, large brittleness and poor long-term reliability. For example, in the sealing and bonding of automotive electronic components such as VVL (variable valve lift) actuators, there are long-term high temperature resistance requirements and severe requirements of high and low temperature impact in extreme environments, and the problems of cracking, poor sealing and the like easily occur in the one-component epoxy resin used as an encapsulating material, which causes product failure.

In order to solve the problems of insufficient heat resistance and large thermal expansion coefficient of the existing epoxy single-component adhesive, the prior art mostly uses multifunctional novolac epoxy resin to improve the heat resistance of the adhesive, for example: the high temperature resistant adhesive disclosed in CN110655891A, the high temperature resistant color-changeable anti-counterfeiting epoxy adhesive disclosed in CN102391810A and the preparation method thereof, the low linear expansion coefficient medium and low temperature cured single-component epoxy adhesive and the preparation method disclosed in CN105670542A and the like, because the heat resistance is improved by increasing the crosslinking density, the brittleness of a cured product is synchronously increased, and the use reliability is reduced. The application of bismaleimide in adhesives is researched a lot, but the bismaleimide is mostly introduced to improve the overall heat resistance, and the performance balance of the whole composition still has an obvious short board.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a high-heat-resistance single-component adhesive and a preparation method thereof. Therefore, the high heat-resistant single-component adhesive with mild curing heat release, high heat resistance of a cured product, high toughness, low thermal expansion coefficient and excellent high and low temperature impact resistance and the preparation method thereof are provided.

The content of the invention is as follows: the high-heat-resistance single-component adhesive is characterized by comprising the following components in parts by weight: the composite material is prepared by mixing 5-30 parts by weight of toughened modified bismaleimide resin, 15-55 parts by weight of epoxy resin, 0.1-5 parts by weight of epoxy active diluent, 3-18 parts by weight of latent curing agent, 0.01-0.5 part by weight of defoaming agent, 0.01-0.5 part by weight of wetting dispersant, 0.1-5 parts by weight of catalyst and 5-60 parts by weight of inorganic filler.

The invention comprises the following steps: the toughened and modified bismaleimide resin is a prepolymerization product of bismaleimide resin and an allyl compound; the bismaleimide resin has a chemical structural formula shown in a formula (I), and the allyl compound is a monoallyl compound or a diallyl compound;

in formula (I): r₁And R₂Is C1-C10 alkyl or aryl; n is 1-400; the bismaleimide resin is a brownish red solid, the softening point (melting point) is 50-110 ℃, and the volatile content is less than or equal to 0.3%.

The allyl compound is any one of diallyl bisphenol A, diallyl bisphenol S, polyallyl ether ketone resin, allyl phenol epoxy resin, allyl linear phenolic resin, N-allyl arylamine compound and silicon modified allyl compound; diallyl bisphenol A is preferred.

The invention comprises the following steps: the epoxy resin is one or a mixture of more than two of glycidyl ether type difunctional epoxy resin, glycidyl ether type multifunctional epoxy resin, toughened and modified glycidyl ether type difunctional epoxy resin and toughened and modified glycidyl ether type multifunctional epoxy resin; the glycidyl ether type difunctional epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether and aliphatic glycidyl ether; the glycidyl ether type multifunctional epoxy resin is phenol type novolac epoxy resin, o-cresol type novolac epoxy resin or bisphenol A type novolac epoxy resin; the toughened and modified epoxy resin is rubber toughened epoxy resin, hyperbranched polymer toughened epoxy resin, thermoplastic resin toughened epoxy resin or thermotropic liquid crystal polymer toughened epoxy resin; the epoxy equivalent of the epoxy resin is 140-350 g/eq, and the viscosity at 25 ℃ is 6-300 Pa.s; bisphenol A epoxy resin and bisphenol A epoxy resin toughened and modified by (core-shell) rubber are preferred.

The invention comprises the following steps: the latent curing agent is a temperature-sensitive curing agent and can be one or a mixture of more than two of dicyandiamide (CVC, OMICURE DDA 5; ADEKA, EH-3842; Yingcao, Dyhard 100S), imidazoles (ADEKA, EH-3293S; ajinomotol, PN-23; complex homonove, HMA-2300), aromatic amines (Xinnasi, 4,4 ' -DDS; Taiji new wood, 4,4 ' -DDS; complex homonove, 3, 3 ' -DDS), organic hydrazides (DDS, adipic dihydrazide; Huntington-Cao, sebacic dihydrazide; Shandongmen, sebacic dihydrazide), organic acid anhydrides (Jiaxing-Bixing, JHY-910; Hitachi, HN-7000A; Nanjing Lin institute, TOA); the dicyandiamide and the imidazole latent curing agent are preferred.

The invention comprises the following steps: the epoxy active diluent is one or a mixture of more than two of benzyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, C12-C14 monoglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether and polypropylene glycol diglycidyl ether; preferably (bifunctional) 1, 4-butanediol diglycidyl ether;

the defoaming agent is one or a mixture of more than two of non-silicon polymer defoaming agents (BYK, BYK-A535, BYK-A501 and BYK-1790), organosilicon polymer compound defoaming agents (BYK, BYK-A530 and BYK-088) and modified organosilicon defoaming agents (BYK, BYK-1796, BYK-A525 and BYK-1615); preferably an organosilicon polymer compound defoaming agent;

the wetting dispersant is a wetting dispersant (BYK, BYK-W940 and BYK-W980) with viscosity reduction and anti-settling functions, or a rheological additive and the wetting dispersant can be compounded (BYK, BYK-W9010, BYK-W9012, GARAMATE-1958 and BYK-7410 ET); the wetting dispersant with viscosity reduction and anti-settling functions is preferred;

the catalyst is one or a mixture of more than two of imidazoles (four nationality chemical, 2E4 MZ-CN; gustatory hormone, PN-23; complex high-tech, HMA-2300), organic ureas (winning, Dyhard UR200, Dyhard UR300 and Dyhard UR500), peroxides (Shandong polychemistry, benzoyl peroxide; Weifang Shandao chemistry, dicumyl peroxide; Xibao biology, dicyclohexyl dicarbonate peroxide); preferably organic ureas, peroxide catalysts;

the inorganic filler is one or two of spherical silica micropowder and boehmite; the spherical silicon micro powder is selected from electronic grade D5010-30 μm and D99 less than 50 μm, and the boehmite is selected from D501.5-3.5 μm and D99 less than 5 μm; preferably, the spherical silicon micro powder is selected from electronic grade D5015-25 μm and D99 < 50 μm, and the boehmite is selected from D502-2.5 μm and D99 < 5 μm.

The high-heat-resistance single-component adhesive can also contain color paste for color matching, flame retardants with different flame-retardant mechanisms, thixotropic regulators, other auxiliaries and the like according to needs.

Another aspect of the invention is: a preparation method of a high heat-resistant single-component adhesive is characterized by comprising the following steps:

a. preparation of bismaleimide resin:

(a) adding 0.1-0.15 mol of maleic anhydride and 200mL of solvent into a reactor (such as a round-bottom flask) provided with a stirrer, a thermometer and a reflux condenser, stirring for dissolving, then (slowly) adding 0.1-0.15 mol of p-aminophenol, reacting for 2-3 h at room temperature, then adding 0.0001-0.001 mol of catalyst, heating for refluxing for 3-4 h, and then cooling, elutriating, filtering, recrystallizing to obtain N- (4-hydroxyphenyl) maleimide;

(b) 0.1mol of N- (4-hydroxyphenyl) maleimide and 100mL of a solvent are charged into a reactor A (for example, a round-bottomed flask) equipped with a stirrer, a thermometer and a reflux condenser, and dissolved by stirring; adding 0.05mol of chlorine-terminated polysiloxane, 50mL of solvent and 0.05-0.2 mol of alkaline substance into another container B to prepare a mixed solution C; slowly dropping the mixed solution C into the reactor A through a constant-pressure dropping funnel at the temperature of 0-10 ℃, reacting at room temperature for 4-5 hours after the dropping is finished, and then carrying out elutriation, filtration and washing to obtain bismaleimide resin;

the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and acetone;

the catalyst is sodium acetate or nickel acetate;

the alkaline substance is pyridine or triethylamine;

the viscosity range vis (25 ℃) of the chlorine-terminated polysiloxane is 5-5000 cSt;

b. toughening modification of bismaleimide resin:

adding 0.1mol of bismaleimide resin into a reactor (such as a three-neck flask), heating to 100-140 ℃ to melt the bismaleimide resin, adding 0.01-0.1 mol of allyl compound, stirring at the constant temperature of 100-140 ℃ for 10-60 min to fully pre-polymerize, discharging, cooling, grinding into powder, (filtering by using a 2000-mesh screen to obtain resin powder with the particle size D50 within 20 mu m), and thus obtaining the toughened modified bismaleimide resin;

the allyl compound is a monoallyl compound or a diallyl compound;

c. preparing a high-heat-resistant single-component adhesive:

preparing materials: taking raw materials of 5-30 parts by weight of toughened modified bismaleimide resin, 15-55 parts by weight of epoxy resin, 0.1-5 parts by weight of epoxy active diluent, 3-18 parts by weight of latent curing agent, 0.01-0.5 part by weight of defoaming agent, 0.01-0.5 part by weight of wetting dispersant, 0.1-5 parts by weight of catalyst and 5-60 parts by weight of inorganic filler;

mixing: firstly, adding epoxy resin, toughened modified bismaleimide resin, an epoxy active diluent, a defoaming agent and a wetting dispersant into a vacuum planetary stirring kettle, starting stirring (fully) and uniformly mixing, adding an inorganic filler, mixing (fully) and uniformly again, adding a latent curing agent and a catalyst when the temperature of materials in the stirring kettle is reduced to normal temperature, starting stirring and vacuum again to uniformly mix the materials and (fully) remove air in the materials, and thus obtaining the high-heat-resistance single-component adhesive.

In another aspect of the invention: the allyl compound in step b may be any one of diallyl bisphenol a, diallyl bisphenol S, polyallyl ether ketone resin, allyl phenol epoxy resin, allyl phenol novolac resin, N-allyl arylamine compound, and silicon-modified allyl compound.

In another aspect of the invention: the epoxy resin is one or a mixture of more than two of glycidyl ether type difunctional epoxy resin, glycidyl ether type multifunctional epoxy resin, toughened and modified glycidyl ether type difunctional epoxy resin and toughened and modified glycidyl ether type multifunctional epoxy resin; the glycidyl ether type difunctional epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether and aliphatic glycidyl ether; the glycidyl ether type multifunctional epoxy resin is phenol type novolac epoxy resin, o-cresol type novolac epoxy resin or bisphenol A type novolac epoxy resin; the toughened and modified epoxy resin is rubber toughened epoxy resin, hyperbranched polymer toughened epoxy resin, thermoplastic resin toughened epoxy resin or thermotropic liquid crystal polymer toughened epoxy resin; the epoxy equivalent of the epoxy resin is 140-350 g/eq, and the viscosity at 25 ℃ is 6-300 Pa.s; bisphenol A epoxy resin and bisphenol A epoxy resin toughened and modified by (core-shell) rubber are preferred.

In another aspect of the invention: the latent curing agent is a temperature-sensitive curing agent and can be one or a mixture of more than two of dicyandiamide (CVC, OMICURE DDA 5; ADEKA, EH-3842; Yingcao, Dyhard 100S), imidazoles (ADEKA, EH-3293S; ajinomotol, PN-23; complex homonove, HMA-2300), aromatic amines (Xinnasi, 4,4 ' -DDS; Taiji new wood, 4,4 ' -DDS; complex homonove, 3, 3 ' -DDS), organic hydrazides (DDS, adipic dihydrazide; Huntington-Cao, sebacic dihydrazide; Shandongmen, sebacic dihydrazide), organic acid anhydrides (Jiaxing-Bixing, JHY-910; Hitachi, HN-7000A; Nanjing Lin institute, TOA); the dicyandiamide and the imidazole latent curing agent are preferred.

In another aspect of the invention: the epoxy active diluent is one or a mixture of more than two of benzyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, C12-C14 monoglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether and polypropylene glycol diglycidyl ether; preferably (bifunctional) 1, 4-butanediol diglycidyl ether;

the defoaming agent is one or a mixture of more than two of non-silicon polymer defoaming agents (BYK, BYK-A535, BYK-A501 and BYK-1790), organosilicon polymer compound defoaming agents (BYK, BYK-A530 and BYK-088) and modified organosilicon defoaming agents (BYK, BYK-1796, BYK-A525 and BYK-1615); preferably an organosilicon polymer compound defoaming agent;

the wetting dispersant is a wetting dispersant (BYK, BYK-W940 and BYK-W980) with viscosity reduction and anti-settling functions, or a rheological additive and the wetting dispersant can be compounded (BYK, BYK-W9010, BYK-W9012, GARAMATE-1958 and BYK-7410 ET); the wetting dispersant with viscosity reduction and anti-settling functions is preferred;

the catalyst is one or a mixture of more than two of imidazoles (four nationality chemical, 2E4 MZ-CN; gustatory hormone, PN-23; complex high-tech, HMA-2300), organic ureas (winning, Dyhard UR200, Dyhard UR300 and Dyhard UR500), peroxides (Shandong polychemistry, benzoyl peroxide; Weifang Shandao chemistry, dicumyl peroxide; Xibao biology, dicyclohexyl dicarbonate peroxide); preferably organic ureas, peroxide catalysts;

the inorganic filler is one or two of spherical silica micropowder and boehmite; the spherical silicon micro powder is selected from electronic grade D5010-30 μm and D99 less than 50 μm, and the boehmite is selected from D501.5-3.5 μm and D99 less than 5 μm; preferably, the spherical silicon micro powder is selected from electronic grade D5015-25 μm and D99 < 50 μm, and the boehmite is selected from D502-2.5 μm and D99 < 5 μm.

The high-heat-resistance single-component adhesive can also contain color paste for color matching, flame retardants with different flame-retardant mechanisms, thixotropic regulators, other auxiliaries and the like according to needs.

The application (use) method of the high heat-resistant single-component adhesive comprises the following steps: after the surface treatment of the device to be bonded and packaged is finished, a proper amount of high-heat-resistance single-component adhesive is dispensed to a proper position through an automatic dispenser or a manual dispenser, then the device is placed in an oven at the temperature of 120-150 ℃ for curing for 30-60 min, and then the device is naturally cooled to the room temperature.

Compared with the prior art, the invention has the following characteristics and beneficial effects:

(1) in the heating curing type single-component adhesive, toughened and modified bismaleimide resin is used, a latent composite curing system with different activation temperature ranges is matched, and high-filling-amount low-stress spherical silica micro powder is used as an auxiliary material; the toughened and modified bismaleimide resin and the epoxy resin are polymerized respectively to form an interpenetrating network structure, so that the toughness of a cured product, especially low-temperature brittleness, is improved; the reaction temperature range of the composite curing system and the toughened bismaleimide resin is wide, the heat release is mild, the surface quality of a cured product is good, and the stress is small; the heat resistance and the dielectric property of the cured product are improved, and the bonding strength of the cured product is not affected;

(2) the invention adopts the bismaleimide resin which is subjected to toughening modification treatment, and the bismaleimide resin, the epoxy resin and the curing agent are cured with different activities to form a cross-linked interpenetrating network structure, and the structure is superposed with the toughening effect of the toughening modified bismaleimide resin, so that the brittleness of a cured product is improved, the high and low temperature impact resistance is improved, and the reliability is enhanced. Meanwhile, the structure of the bismaleimide resin improves the heat resistance indexes such as Tg, Td and the like of the whole cured product;

(3) after being cured at 120 ℃/30min, the high-heat-resistant single-component adhesive has smooth and good surface, Shore D hardness of more than 80, Tg of more than 145 ℃, Td (5%) of more than 345 ℃, shear bonding strength of 20MPa, no failure after being impacted for 10 times of-40 ℃/1 h-135 ℃/1h, and no crack at a bonding interface, and can be applied to bonding and sealing of electronic and electrical components, metal and non-metal devices with heat resistance and environmental temperature requirements;

(4) the high-heat-resistance single-component adhesive has the characteristics of mild curing process, high heat resistance of a cured product, high toughness, low thermal expansion coefficient, excellent high and low temperature impact resistance and the like; the product has simple preparation process, simple and convenient working procedure, easy operation and strong practicability.

Detailed Description

The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.

A preparation method of a high-heat-resistance single-component adhesive comprises the following steps:

preparation of the first part of bismaleimide resin

Examples 1-1 to 1-5: preparation of bismaleimide resin

The implementation steps are as follows:

(a) adding 0.1-0.15 mol of maleic anhydride and 200ml of solvent into a round-bottom flask equipped with a stirrer, a thermometer and a reflux condenser, stirring for dissolving, then slowly adding 0.1-0.15 mol of p-aminophenol, reacting for 2-3 h at room temperature, then adding 0.0001-0.001 mol of catalyst, heating for refluxing for 3-4 h, then cooling, elutriating, filtering, and recrystallizing to obtain N- (4-hydroxyphenyl) maleimide;

(b) adding 0.1mol of N- (4-hydroxyphenyl) maleimide and 100mL of solvent into a round-bottom flask A which is provided with a stirrer, a thermometer and a reflux condenser, and stirring for dissolving; adding 0.05mol of chlorine-terminated polysiloxane, 50mL of solvent and 0.05-0.2 mol of alkaline substance into another container B to prepare a mixed solution C; slowly dropping the mixed solution C into the round-bottom flask A through a constant-pressure dropping funnel at the temperature of 0-10 ℃, reacting at room temperature for 4-5 hours after the dropping is finished, and then carrying out elutriation, filtration and washing to obtain the bismaleimide resin.

The solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and acetone;

the catalyst is sodium acetate or nickel acetate;

the alkaline substance is one or more of pyridine and triethylamine.

The chlorine-terminated polysiloxane is selected from the viscosity range vis (25 ℃) 5-5000 cSt.

Table 1: the specific composition ratio of the bismaleimide resin prepared in the embodiment 1-5 is as follows:

toughening modification of second part bismaleimide resin

Examples 2-1 to 2-7: preparation of toughened and modified bismaleimide resin

The implementation steps are as follows:

adding 0.1mol of bismaleimide resin into a three-neck flask, heating to 100-140 ℃ to melt the bismaleimide resin, adding 0.01-0.1 mol of allyl compound, stirring at 100-140 ℃ for 10-60 min at constant temperature to fully pre-polymerize the allylic compound, discharging, cooling, grinding into powder, and filtering by using a 2000-mesh screen to obtain resin powder with the particle size D50 within 20 mu m.

The allyl compound is selected from 2,2' -diallyl bisphenol A or 2-allyl phenol.

Example 2 starting materials used:

a1: the bismaleimide resin prepared in example 1-1;

a2: bismaleimide resins prepared in examples 1-2;

a3 bismaleimide resin prepared as in examples 1-3;

a4: bismaleimide resins prepared in examples 1-4;

a5: bismaleimide resins prepared in examples 1-5;

table 2: the specific composition ratio of the toughened and modified bismaleimide resin prepared in the embodiment 2-1-2-7 is as follows:

preparation and application of high-heat-resistance single-component adhesive of third part

Examples 3-1 to 3-7: preparation of high-heat-resistance single-component adhesive

The implementation steps are as follows:

firstly, adding epoxy resin, toughened modified bismaleimide resin, an epoxy active diluent, a defoaming agent and a dispersing wetting agent into a vacuum planetary stirring kettle, starting stirring, fully mixing uniformly, adding an inorganic filler, fully mixing uniformly again, adding a latent curing agent and an accelerant when the temperature of materials in the kettle is reduced to normal temperature, starting stirring and vacuum again to fully mix the materials uniformly and fully remove air in the materials, and thus obtaining the high-heat-resistance single-component adhesive.

The application method of the high-heat-resistance single-component adhesive comprises the following steps: after the surface treatment of the device to be bonded and packaged is finished, a proper amount of adhesive is dispensed to a proper position through an automatic dispenser or a manual dispenser, the device is placed in an oven at the temperature of 120-150 ℃ for curing for 30-60 min, and then the device is naturally cooled to the room temperature.

The raw materials used in the implementation are:

b1: the toughened modified bismaleimide resin prepared in example 2-1;

b2: the toughened modified bismaleimide resin prepared in example 2-2;

b3: the toughened modified bismaleimide resin prepared in examples 2-3;

b4: the toughened modified bismaleimide resin prepared in examples 2-4;

b5: the toughened modified bismaleimide resin prepared in examples 2-5;

b6: the toughened modified bismaleimide resins prepared in examples 2-6;

b7: toughened modified bismaleimide resins prepared in examples 2-7;

c1: 850S of epoxy resin, 194g/eq of blue-through star, 184-equivalent epoxy, 11000-equivalent epoxy-equivalent at 25 ℃ at 15000 mPa.s;

c2 epoxy resin YD-127, Kunshan chemical engineering, epoxy equivalent 180-;

c3: core-shell rubber toughened epoxy resin, MX-125, a Brillouin chemistry;

c4: o-cresol novolac epoxy resin, YDCN-500-1P, Kunshan nationwide chemical engineering;

d1: diluent 1, 4-butanediol diglycidyl ether, XY622, anxinyu;

d2: diluent C12-C14 monoglycidyl ether, XY748, Anhuixuan;

e1: defoamer BYK-530, birk chemical;

e2: defoamer BYK-a 535, birk chemical;

f1: wetting dispersant BYK-9010, Pico chemical;

f2: wetting dispersant BYK-W940, Pico chemical;

g1: spherical silicon micropowder DQ1028L, Jiangsu birry;

g2: boehmite, BG-613, Anhui Shitong;

h1: latent curative OMICURE DDA 5, CVC;

h2: latent curing agent FXR-1020, Taiwan III and synthetic shares;

i1: organic urea accelerator, UR500, winning chemistry;

i2: benzoyl peroxide, BPO, shanghai kelin chemical industry.

Table 3: example 3-1-3-7 specific composition ratios of the high heat-resistant single-component adhesive are as follows:

table 4: examples 3-1 to 3-7 table of performance parameters of the high heat-resistant single-component adhesive:

note: the solidification condition is 120 ℃/0.5h, and the temperature is reduced and cooled to the room temperature. After cold and hot impact, the resin on the surface of the sample device is not cracked, and the non-peeling at the joint of the resin and the device is expressed as excellent; the sample devices had slight cracking of the resin on the surface, or slight peeling of the resin from the junction with the device was marked as O (defects < 1mm in length and < 5 in number were considered slight); the samples were marked by severe cracking of the resin on the surface of the device, or severe delamination of the resin from the device junction as Δ (defects with a length > 1mm or a number > 5 were considered severe).

Comparative example of the fourth section

Comparative example the same procedure as in example 3 was conducted.

A6: bismaleimide resin, BMI-01, hong lake bismaleimide;

a7 toughened bismaleimide resin, SM003, Honghu bismaleimide.

Table 5: comparative examples 4-1 to 4-7 bismaleimide resin composition ratios:

table 6: comparative examples 4-1 to 4-7 one-component adhesives the performance parameters are given in the table:

note: the solidification condition is 120 ℃/0.5h, and the temperature is reduced and cooled to the room temperature. After cold and hot impact, the resin on the surface of the sample device is not cracked, and the non-peeling at the joint of the resin and the device is expressed as excellent; the sample devices had slight cracking of the resin on the surface, or slight peeling of the resin from the junction with the device was marked as O (defects < 1mm in length and < 5 in number were considered slight); the samples were marked by severe cracking of the resin on the surface of the device, or severe delamination of the resin from the device junction as Δ (defects with a length > 1mm or a number > 5 were considered severe).

Example 4:

the high-heat-resistance single-component adhesive is prepared by mixing 5 parts by weight of toughened modified bismaleimide resin, 15 parts by weight of epoxy resin, 0.1 part by weight of epoxy active diluent, 3 parts by weight of latent curing agent, 0.01 part by weight of defoaming agent, 0.01 part by weight of wetting dispersant, 0.1 part by weight of catalyst and 5 parts by weight of inorganic filler.

Example 5:

the high-heat-resistance single-component adhesive is prepared by mixing 30 parts by weight of toughened and modified bismaleimide resin, 55 parts by weight of epoxy resin, 5 parts by weight of epoxy active diluent, 18 parts by weight of latent curing agent, 0.5 part by weight of defoaming agent, 0.5 part by weight of wetting dispersant, 5 parts by weight of catalyst and 60 parts by weight of inorganic filler.

Example 6:

the high-heat-resistance single-component adhesive is prepared by mixing 18 parts by weight of toughened modified bismaleimide resin, 35 parts by weight of epoxy resin, 2.5 parts by weight of epoxy active diluent, 11 parts by weight of latent curing agent, 0.25 part by weight of defoaming agent, 0.25 part by weight of wetting dispersant, 2.5 parts by weight of catalyst and 32 parts by weight of inorganic filler.

Example 7:

the high-heat-resistance single-component adhesive is prepared by mixing 11 parts by weight of toughened modified bismaleimide resin, 25 parts by weight of epoxy resin, 0.9 part by weight of epoxy active diluent, 8 parts by weight of latent curing agent, 0.11 part by weight of defoaming agent, 0.15 part by weight of wetting dispersant, 1.5 parts by weight of catalyst and 26 parts by weight of inorganic filler.

Example 8:

the high-heat-resistance single-component adhesive is prepared by mixing 26 parts by weight of toughened modified bismaleimide resin, 48 parts by weight of epoxy resin, 4 parts by weight of epoxy active diluent, 15 parts by weight of latent curing agent, 0.38 part by weight of defoaming agent, 0.35 part by weight of wetting dispersant, 4 parts by weight of catalyst and 55 parts by weight of inorganic filler.

In the above embodiments 4 to 8:

the toughened and modified bismaleimide resin is a prepolymerization product of bismaleimide resin and an allyl compound; the bismaleimide resin has a chemical structural formula shown in a formula (I), and the allyl compound is a monoallyl compound or a diallyl compound;

in formula (I): r₁And R₂Is C1-C10 alkyl or aryl; n is 1-400; the bismaleimide resin is a brownish red solid, the softening point (melting point) is 50-110 ℃, and the volatile content is less than or equal to 0.3%.

The allyl compound is any one of diallyl bisphenol A, diallyl bisphenol S, polyallyl ether ketone resin, allyl phenol epoxy resin, allyl linear phenolic resin and N-allyl arylamine compound, and silicon modified allyl compound; diallyl bisphenol A is preferred.

In the above embodiments 4 to 8: the epoxy resin is one or a mixture of more than two of glycidyl ether type difunctional epoxy resin, glycidyl ether type multifunctional epoxy resin, toughened and modified glycidyl ether type difunctional epoxy resin and toughened and modified glycidyl ether type multifunctional epoxy resin; the glycidyl ether type difunctional epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether and aliphatic glycidyl ether; the glycidyl ether type multifunctional epoxy resin is phenol type novolac epoxy resin, o-cresol type novolac epoxy resin or bisphenol A type novolac epoxy resin; the toughened and modified epoxy resin is rubber toughened epoxy resin, hyperbranched polymer toughened epoxy resin, thermoplastic resin toughened epoxy resin or thermotropic liquid crystal polymer toughened epoxy resin; the epoxy equivalent of the epoxy resin is 140-350 g/eq, and the viscosity at 25 ℃ is 6-300 Pa.s; bisphenol A epoxy resin and bisphenol A epoxy resin toughened and modified by (core-shell) rubber are preferred.

In the above embodiments 4 to 8: the latent curing agent is a temperature-sensitive curing agent and can be one or a mixture of more than two of dicyandiamide (CVC, OMICURE DDA 5; ADEKA, EH-3842; Yingcao, Dyhard 100S), imidazoles (ADEKA, EH-3293S; ajinomotol, PN-23; complex homonove, HMA-2300), aromatic amines (Xinnasi, 4,4 ' -DDS; Taiji new wood, 4,4 ' -DDS; complex homonove, 3, 3 ' -DDS), organic hydrazides (DDS, adipic dihydrazide; Huntington-Cao, sebacic dihydrazide; Shandongmen, sebacic dihydrazide), organic acid anhydrides (Jiaxing-Bixing, JHY-910; Hitachi, HN-7000A; Nanjing Lin institute, TOA); the dicyandiamide and the imidazole latent curing agent are preferred.

In the above embodiments 4 to 8:

the epoxy active diluent is one or a mixture of more than two of benzyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, C12-C14 monoglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether and polypropylene glycol diglycidyl ether; preferably (bifunctional) 1, 4-butanediol diglycidyl ether;

the defoaming agent is one or a mixture of more than two of non-silicon polymer defoaming agents (BYK, BYK-A535, BYK-A501 and BYK-1790), organosilicon polymer compound defoaming agents (BYK, BYK-A530 and BYK-088) and modified organosilicon defoaming agents (BYK, BYK-1796, BYK-A525 and BYK-1615); preferably an organosilicon polymer compound defoaming agent;

the wetting dispersant is a wetting dispersant (BYK, BYK-W940 and BYK-W980) with viscosity reduction and anti-settling functions, or a rheological additive and the wetting dispersant can be compounded (BYK, BYK-W9010, BYK-W9012, GARAMATE-1958 and BYK-7410 ET); the wetting dispersant with viscosity reduction and anti-settling functions is preferred;

the catalyst is one or a mixture of more than two of imidazoles (four nationality chemical, 2E4 MZ-CN; gustatory hormone, PN-23; complex high-tech, HMA-2300), organic ureas (winning, Dyhard UR200, Dyhard UR300 and Dyhard UR500), peroxides (Shandong polychemistry, benzoyl peroxide; Weifang Shandao chemistry, dicumyl peroxide; Xibao biology, dicyclohexyl dicarbonate peroxide); preferably organic ureas, peroxide catalysts;

the inorganic filler is one or two of spherical silica micropowder and boehmite; the spherical silicon micro powder is selected from electronic grade D5010-30 μm and D99 less than 50 μm, and the boehmite is selected from D501.5-3.5 μm and D99 less than 5 μm; preferably, the spherical silicon micro powder is selected from electronic grade D5015-25 μm and D99 < 50 μm, and the boehmite is selected from D502-2.5 μm and D99 < 5 μm.

The high-heat-resistance single-component adhesive of embodiments 4 to 8 may further include color pastes for color matching, flame retardants with different flame-retardant mechanisms, thixotropic regulators, other additives, and the like as needed.

Example 9:

a preparation method of a high-heat-resistance single-component adhesive comprises the following steps:

a. preparation of bismaleimide resin:

(a) adding 0.13mol of maleic anhydride and 200mL of solvent into a reactor (such as a round-bottom flask) provided with a stirrer, a thermometer and a reflux condenser, stirring for dissolving, then (slowly) adding 0.13mol of p-aminophenol, reacting for 2.5h at room temperature, then adding 0.0005mol of catalyst, heating for refluxing for 3.5h, then cooling, elutriating, filtering by suction and recrystallizing to obtain N- (4-hydroxyphenyl) maleimide;

(b) 0.1mol of N- (4-hydroxyphenyl) maleimide and 100mL of a solvent are charged into a reactor A (for example, a round-bottomed flask) equipped with a stirrer, a thermometer and a reflux condenser, and dissolved by stirring; adding 0.05mol of chlorine-terminated polysiloxane, 50mL of solvent and 0.12mol of alkaline substance into another container B to prepare a mixed solution C; slowly dropping the mixed solution C into the reactor A through a constant-pressure dropping funnel at the temperature of 5 ℃, reacting for 4.5 hours at room temperature after the dropping is finished, and then carrying out elutriation, filtration and washing to prepare bismaleimide resin;

the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and acetone;

the catalyst is sodium acetate or nickel acetate;

the alkaline substance is pyridine or triethylamine;

the viscosity range vis (25 ℃) of the chlorine-terminated polysiloxane is 5-5000 cSt;

b. toughening modification of bismaleimide resin:

adding 0.1mol of bismaleimide resin into a reactor (such as a three-neck flask), heating to 120 ℃ to melt the bismaleimide resin, adding 0.05mol of allyl compound, stirring at the constant temperature of 120 ℃ for 35min to fully pre-polymerize, discharging and cooling, grinding into powder, (and filtering by using a 2000-mesh screen to obtain resin powder with the particle size D50 within 20 mu m), namely obtaining the prepared toughened modified bismaleimide resin;

the allyl compound is a monoallyl compound or a diallyl compound;

c. preparing a high-heat-resistant single-component adhesive:

preparing materials: taking raw materials of 5-30 parts by weight of toughened modified bismaleimide resin, 15-55 parts by weight of epoxy resin, 0.1-5 parts by weight of epoxy active diluent, 3-18 parts by weight of latent curing agent, 0.01-0.5 part by weight of defoaming agent, 0.01-0.5 part by weight of wetting dispersant, 0.1-5 parts by weight of catalyst and 5-60 parts by weight of inorganic filler; the specific weight parts of the use amount are the same as any one of the above embodiments 4 to 8:

mixing: firstly, adding epoxy resin, toughened modified bismaleimide resin, an epoxy active diluent, a defoaming agent and a wetting dispersant into a vacuum planetary stirring kettle, starting stirring (fully) and uniformly mixing, adding an inorganic filler, mixing (fully) and uniformly again, adding a latent curing agent and a catalyst when the temperature of materials in the stirring kettle is reduced to normal temperature, starting stirring and vacuum again to uniformly mix the materials and (fully) remove air in the materials, and thus obtaining the high-heat-resistance single-component adhesive.

Example 10:

a preparation method of a high-heat-resistance single-component adhesive comprises the following steps:

a. preparation of bismaleimide resin:

(a) adding 0.1mol of maleic anhydride and 200mL of solvent into a reactor (such as a round-bottom flask) provided with a stirrer, a thermometer and a reflux condenser, stirring for dissolving, then (slowly) adding 0.1mol of p-aminophenol, reacting for 2 hours at room temperature, then adding 0.0001mol of catalyst, heating for refluxing for 3 hours, then cooling, elutriating, filtering by suction, and recrystallizing to obtain N- (4-hydroxyphenyl) maleimide;

(b) 0.1mol of N- (4-hydroxyphenyl) maleimide and 100mL of a solvent are charged into a reactor A (for example, a round-bottomed flask) equipped with a stirrer, a thermometer and a reflux condenser, and dissolved by stirring; adding 0.05mol of chlorine-terminated polysiloxane, 50mL of solvent and 0.05mol of alkaline substance into another container B to prepare a mixed solution C; slowly dropping the mixed solution C into the reactor A through a constant-pressure dropping funnel at the temperature of 0 ℃, reacting for 4 hours at room temperature after the dropping is finished, and then performing elutriation, filtration and washing to prepare bismaleimide resin;

the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and acetone;

the catalyst is sodium acetate or nickel acetate;

the alkaline substance is pyridine or triethylamine;

the viscosity range vis (25 ℃) of the chlorine-terminated polysiloxane is 5-5000 cSt;

b. toughening modification of bismaleimide resin:

adding 0.1mol of bismaleimide resin into a reactor (such as a three-neck flask), heating to 100 ℃ to melt the bismaleimide resin, adding 0.01mol of allyl compound, stirring at the constant temperature of 100 ℃ for 60min to fully pre-polymerize, discharging and cooling, grinding into powder, (and filtering by using a 2000-mesh screen to obtain resin powder with the particle size D50 within 20 mu m), namely obtaining the prepared toughened modified bismaleimide resin;

the allyl compound is a monoallyl compound or a diallyl compound;

c. preparing a high-heat-resistant single-component adhesive:

preparing materials: taking raw materials of 5 parts by weight of toughened modified bismaleimide resin, 15 parts by weight of epoxy resin, 0.1 part by weight of epoxy active diluent, 3 parts by weight of latent curing agent, 0.01 part by weight of defoaming agent, 0.01 part by weight of wetting dispersant, 0.1 part by weight of catalyst and 5 parts by weight of inorganic filler;

mixing: firstly, adding epoxy resin, toughened modified bismaleimide resin, an epoxy active diluent, a defoaming agent and a wetting dispersant into a vacuum planetary stirring kettle, starting stirring (fully) and uniformly mixing, adding an inorganic filler, mixing (fully) and uniformly again, adding a latent curing agent and a catalyst when the temperature of materials in the stirring kettle is reduced to normal temperature, starting stirring and vacuum again to uniformly mix the materials and (fully) remove air in the materials, and thus obtaining the high-heat-resistance single-component adhesive.

Example 11:

a preparation method of a high-heat-resistance single-component adhesive comprises the following steps:

a. preparation of bismaleimide resin:

(a) adding 0.15mol of maleic anhydride and 200mL of solvent into a reactor (such as a round-bottom flask) provided with a stirrer, a thermometer and a reflux condenser, stirring for dissolving, then (slowly) adding 0.15mol of p-aminophenol, reacting for 3 hours at room temperature, then adding 0.001mol of catalyst, heating for refluxing for 4 hours, then cooling, elutriating, filtering by suction, and recrystallizing to obtain N- (4-hydroxyphenyl) maleimide;

(b) 0.1mol of N- (4-hydroxyphenyl) maleimide and 100mL of a solvent are charged into a reactor A (for example, a round-bottomed flask) equipped with a stirrer, a thermometer and a reflux condenser, and dissolved by stirring; adding 0.05mol of chlorine-terminated polysiloxane, 50mL of solvent and 0.2mol of alkaline substance into another container B to prepare a mixed solution C; slowly dropping the mixed solution C into the reactor A through a constant-pressure dropping funnel at the temperature of 10 ℃, reacting for 5 hours at room temperature after the dropping is finished, and then performing elutriation, filtration and washing to prepare bismaleimide resin;

the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and acetone;

the catalyst is sodium acetate or nickel acetate;

the alkaline substance is pyridine or triethylamine;

the viscosity range vis (25 ℃) of the chlorine-terminated polysiloxane is 5-5000 cSt;

b. toughening modification of bismaleimide resin:

adding 0.1mol of bismaleimide resin into a reactor (such as a three-neck flask), heating to 140 ℃ to melt the bismaleimide resin, adding 0.1mol of allyl compound, stirring at the constant temperature of 140 ℃ for 10min to fully pre-polymerize, discharging and cooling, grinding into powder, (and filtering by using a 2000-mesh screen to obtain resin powder with the particle size D50 within 20 mu m), namely obtaining the prepared toughened modified bismaleimide resin;

the allyl compound is a monoallyl compound or a diallyl compound;

c. preparing a high-heat-resistant single-component adhesive:

preparing materials: taking raw materials of 30 parts by weight of toughened modified bismaleimide resin, 55 parts by weight of epoxy resin, 5 parts by weight of epoxy active diluent, 18 parts by weight of latent curing agent, 0.5 part by weight of defoaming agent, 0.5 part by weight of wetting dispersant, 5 parts by weight of catalyst and 60 parts by weight of inorganic filler;

mixing: firstly, adding epoxy resin, toughened modified bismaleimide resin, an epoxy active diluent, a defoaming agent and a wetting dispersant into a vacuum planetary stirring kettle, starting stirring (fully) and uniformly mixing, adding an inorganic filler, mixing (fully) and uniformly again, adding a latent curing agent and a catalyst when the temperature of materials in the stirring kettle is reduced to normal temperature, starting stirring and vacuum again to uniformly mix the materials and (fully) remove air in the materials, and thus obtaining the high-heat-resistance single-component adhesive.

Example 12:

a preparation method of a high-heat-resistance single-component adhesive comprises the following steps:

a. preparation of bismaleimide resin:

(a) adding 0.13mol of maleic anhydride and 200mL of solvent into a reactor (such as a round-bottom flask) provided with a stirrer, a thermometer and a reflux condenser, stirring for dissolving, then (slowly) adding 0.13mol of p-aminophenol, reacting for 2.6h at room temperature, then adding 0.0006mol of catalyst, heating for refluxing for 3.5h, then cooling, elutriating, filtering by suction and recrystallizing to prepare the N- (4-hydroxyphenyl) maleimide;

(b) 0.1mol of N- (4-hydroxyphenyl) maleimide and 100mL of a solvent are charged into a reactor A (for example, a round-bottomed flask) equipped with a stirrer, a thermometer and a reflux condenser, and dissolved by stirring; adding 0.05mol of chlorine-terminated polysiloxane, 50mL of solvent and 0.13mol of alkaline substance into another container B to prepare a mixed solution C; slowly dropping the mixed solution C into the reactor A through a constant-pressure dropping funnel at the temperature of 6 ℃, reacting for 4.6 hours at room temperature after the dropping is finished, and then carrying out elutriation, filtration and washing to prepare bismaleimide resin;

the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and acetone;

the catalyst is sodium acetate or nickel acetate;

the alkaline substance is pyridine or triethylamine;

the viscosity range vis (25 ℃) of the chlorine-terminated polysiloxane is 5-5000 cSt;

b. toughening modification of bismaleimide resin:

adding 0.1mol of bismaleimide resin into a reactor (such as a three-neck flask), heating to 125 ℃ to melt the bismaleimide resin, adding 0.06mol of allyl compound, stirring at 120 ℃ for 40min at constant temperature to fully pre-polymerize the bismaleimide resin, discharging and cooling, grinding into powder, (and filtering by a 2000-mesh screen to obtain resin powder with the particle size D50 within 20 mu m), namely obtaining the prepared toughened modified bismaleimide resin;

the allyl compound is a monoallyl compound or a diallyl compound;

c. preparing a high-heat-resistant single-component adhesive:

preparing materials: taking raw materials of 27 parts by weight of toughened modified bismaleimide resin, 35 parts by weight of epoxy resin, 2.6 parts by weight of epoxy active diluent, 10.5 parts by weight of latent curing agent, 0.26 part by weight of defoaming agent, 0.25 part by weight of wetting dispersant, 2.6 parts by weight of catalyst and 32.5 parts by weight of inorganic filler;

mixing: firstly, adding epoxy resin, toughened modified bismaleimide resin, an epoxy active diluent, a defoaming agent and a wetting dispersant into a vacuum planetary stirring kettle, starting stirring (fully) and uniformly mixing, adding an inorganic filler, mixing (fully) and uniformly again, adding a latent curing agent and a catalyst when the temperature of materials in the stirring kettle is reduced to normal temperature, starting stirring and vacuum again to uniformly mix the materials and (fully) remove air in the materials, and thus obtaining the high-heat-resistance single-component adhesive.

In the above embodiments 9 to 12: the allyl compound in step b may be any one of diallyl bisphenol a, diallyl bisphenol S, polyallyl ether ketone resin, allyl phenol epoxy resin, allyl phenol novolac resin, N-allyl arylamine compound, and silicon-modified allyl compound.

In the above embodiments 9 to 12: the epoxy resin is one or a mixture of more than two of glycidyl ether type difunctional epoxy resin, glycidyl ether type multifunctional epoxy resin, toughened and modified glycidyl ether type difunctional epoxy resin and toughened and modified glycidyl ether type multifunctional epoxy resin; the glycidyl ether type difunctional epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether and aliphatic glycidyl ether; the glycidyl ether type multifunctional epoxy resin is phenol type novolac epoxy resin, o-cresol type novolac epoxy resin or bisphenol A type novolac epoxy resin; the toughened and modified epoxy resin is rubber toughened epoxy resin, hyperbranched polymer toughened epoxy resin, thermoplastic resin toughened epoxy resin or thermotropic liquid crystal polymer toughened epoxy resin; the epoxy equivalent of the epoxy resin is 140-350 g/eq, and the viscosity at 25 ℃ is 6-300 Pa.s; bisphenol A epoxy resin and bisphenol A epoxy resin toughened and modified by (core-shell) rubber are preferred.

In the above embodiments 9 to 12: the latent curing agent is a temperature-sensitive curing agent and can be one or a mixture of more than two of dicyandiamide (CVC, OMICURE DDA 5; ADEKA, EH-3842; Yingcao, Dyhard 100S), imidazoles (ADEKA, EH-3293S; ajinomotol, PN-23; complex homonove, HMA-2300), aromatic amines (Xinnasi, 4,4 ' -DDS; Taiji new wood, 4,4 ' -DDS; complex homonove, 3, 3 ' -DDS), organic hydrazides (DDS, adipic dihydrazide; Huntington-Cao, sebacic dihydrazide; Shandongmen, sebacic dihydrazide), organic acid anhydrides (Jiaxing-Bixing, JHY-910; Hitachi, HN-7000A; Nanjing Lin institute, TOA); the dicyandiamide and the imidazole latent curing agent are preferred.

In the above embodiments 9 to 12:

the epoxy active diluent is one or a mixture of more than two of benzyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, C12-C14 monoglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether and polypropylene glycol diglycidyl ether; preferably (bifunctional) 1, 4-butanediol diglycidyl ether;

the defoaming agent is one or a mixture of more than two of non-silicon polymer defoaming agents (BYK, BYK-A535, BYK-A501 and BYK-1790), organosilicon polymer compound defoaming agents (BYK, BYK-A530 and BYK-088) and modified organosilicon defoaming agents (BYK, BYK-1796, BYK-A525 and BYK-1615); preferably an organosilicon polymer compound defoaming agent;

the wetting dispersant is a wetting dispersant (BYK, BYK-W940 and BYK-W980) with viscosity reduction and anti-settling functions, or a rheological additive and the wetting dispersant can be compounded (BYK, BYK-W9010, BYK-W9012, GARAMATE-1958 and BYK-7410 ET); the wetting dispersant with viscosity reduction and anti-settling functions is preferred;

the catalyst is one or a mixture of more than two of imidazoles (four nationality chemical, 2E4 MZ-CN; gustatory hormone, PN-23; complex high-tech, HMA-2300), organic ureas (winning, Dyhard UR200, Dyhard UR300 and Dyhard UR500), peroxides (Shandong polychemistry, benzoyl peroxide; Weifang Shandao chemistry, dicumyl peroxide; Xibao biology, dicyclohexyl dicarbonate peroxide); preferably organic ureas, peroxide catalysts;

the inorganic filler is one or two of spherical silica micropowder and boehmite; the spherical silicon micro powder is selected from electronic grade D5010-30 μm and D99 less than 50 μm, and the boehmite is selected from D501.5-3.5 μm and D99 less than 5 μm; preferably, the spherical silicon micro powder is selected from electronic grade D5015-25 μm and D99 < 50 μm, and the boehmite is selected from D502-2.5 μm and D99 < 5 μm.

In the high heat-resistant single-component adhesive of embodiments 9 to 12: the flame-retardant color paste can also contain color paste for color matching, flame retardants with different flame-retardant mechanisms, thixotropic regulators, other auxiliary agents and other components according to the needs.

The application (use) method of the high heat-resistant single-component adhesive prepared in the above embodiments 9 to 12 is as follows: after the surface treatment of the device to be bonded and packaged is finished, a proper amount of high-heat-resistance single-component adhesive is dispensed to a proper position through an automatic dispenser or a manual dispenser, then the device is placed in an oven at the temperature of 120-150 ℃ for curing for 30-60 min, and then the device is naturally cooled to the room temperature.

The relevant criteria used for the technical indicators herein are as follows:

viscosity: testing according to GB/T2794-2013 'Single-cylinder rotational viscometer method for measuring viscosity of adhesives';

glass transition temperature measured according to ISO11357-3, Differential Scanning Calorimetry (DSC) part 3, determination of melting and crystallization enthalpies and temperatures;

thermal decomposition temperature: testing according to GB/T27761-;

coefficient of thermal expansion: tested according to ISO11359-2, section 2 of thermomechanical analysis (TMA), determination of the linear thermal expansion coefficient and the glass transition temperature;

shore D hardness: testing according to GB/T2411-2008 using a hardness tester for testing indentation hardness of plastics and hard rubber;

shear adhesion strength: testing according to GB/T7124-;

cold and hot impact: according to GB/T2423.22-2012 environmental test part 2: test methods test N: temperature variation test, the switching is completed within 2min at high temperature and low temperature, and the switching time is-40 ℃/1 h-135 ℃/1 h.

In the above embodiment: the percentages used, not specifically noted, are weight (mass) percentages or percentages known to those skilled in the art; the proportions used, not specifically noted, are weight (mass) proportions; the parts by weight may each be grams or kilograms.

In the above embodiment: the process parameters (temperature, time, etc.) and the numerical values of the components in each step are in the range, and any point can be applicable.

The present invention and the technical contents not specifically described in the above examples are the same as those of the prior art, and the raw materials are all commercially available products.

The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.