Aminophenyl co-modified silicone oil, preparation method thereof and adhesive

Abstract

The invention discloses amino-phenyl co-modified silicone oil, a preparation method thereof and an adhesive. The amino-modified methyl phenyl silicone oil structurally contains a phenyl group structure and an amino group structure at the same time; the structural general formula is as follows: (R1R2R3SiO1 / 2) a (R4R5SiO) b (R6R7SiO) c (R8R9R10SiO1 / 2) d, the preparation method comprises the following steps: (1) weighing the following components in parts by weight: 2.4-10 parts of amino siloxane; 36.5 to 73 parts of phenyl silane or phenyl siloxane; 35.5 to 50 parts of alkyl silane or alkyl siloxane; 0.8-1 part of a quaternary ammonium catalyst; 0 to 12 parts of deionized water; (2) adding the amino siloxane, the phenyl silane or phenyl siloxane, the alkyl silane or alkyl siloxane, the quaternary ammonium catalyst and the deionized water which are weighed in the step (1) into a reactor, and keeping the temperature of 80-100 DEG C for 0.5-1.5 hours in a nitrogen environment; (3) continuously heating to 95-100 DEG C, and carrying out reflux reaction for 3.5-4.5 hours; (4) heating to 145-150 DEG C, and stirring for 1-1.5 hours; and 5) filtering the precipitate, and carrying out rotary evaporation on the liquid to remove low-boiling-point substances, thereby obtaining the product, namely the aminophenyl co-modified silicone oil temperature-resistant agent. Relates to the technical field of macromolecules.

Description

Technical Field

[0001] This application relates to the field of polymer technology, specifically to an aminophenyl co-modified silicone oil, its preparation method, and an adhesive. Background Technology

[0002] Epoxy adhesives are made primarily of epoxy resin, with the addition of curing agents, toughening agents, fillers, and other components, through mixing and curing processes. They possess high bonding strength, heat resistance, chemical corrosion resistance, and electrical insulation properties, and are widely used in electronics, electrical appliances, aerospace, and automotive manufacturing. However, the performance of existing epoxy adhesives may be affected under certain specific application environments, such as high temperature, high humidity, or strong acid / alkali conditions, limiting their application range. In recent years, research has attempted to modify epoxy resins with silicone oil to improve the high-temperature resistance of adhesives. For example, Chinese patent CN201911387628.0 discloses a method for preparing hydroxyl-terminated polymethylphenylsiloxane using polydimethylsiloxane and methylphenylsiloxane as raw materials. The product can effectively improve the storage stability and processing performance of silicone rubber, and optimize the high and low temperature resistance of its vulcanized products. However, conventional hydroxyl-terminated silicone oils have poor compatibility with epoxy resins, and even after blending, they still suffer from easy phase separation, failing to achieve a stable and uniform crosslinking network of silicone-modified epoxy resin within the adhesive layer after curing. Therefore, designing silicone oils with structures similar to epoxy resins for modification can further improve the performance of epoxy adhesives.

[0003] Amino silicone oils are a type of modified silicone oil in which some methyl groups (side-position or terminal-position) are replaced by amino groups. Besides retaining the hydrophobicity and release properties of dimethyl silicone oil, these silicone oils also possess lubricity and softening properties, making them widely applicable in softeners, polishing agents, and coating additives. Depending on the substitution position of the amino groups, amino silicone oils mainly include side-chain amino silicone oils and terminal amino silicone oils. Side-chain amino silicone oils have a high amino content, which can easily cause excessive crosslinking of epoxy resins, leading to embrittlement of the adhesive layer; therefore, they cannot be used in conjunction with amine catalysts. Terminal amino silicone oils typically have amino groups located at one or both ends of the polysiloxane chain, with a lower amino content. Appropriate addition to epoxy adhesives can introduce organosilicon segments while reducing the crosslinking density of the epoxy adhesive and improving the flexibility of the adhesive layer. Early terminal amino silicone oils often used amino-terminated polysiloxanes as precursors, prepared through living polymerization-condensation, catalytic equilibrium, or platinum hydroaddition methods. However, the living polymerization-condensation process is complex and has a long reaction time, with the preparation cycle usually exceeding 24 hours; while the platinum hydroaddition method first prepares terminal hydrogen silicone oil, then mixes it with unsaturated amine compounds such as allylamine and adds it under the action of a platinum catalyst to obtain terminal amino silicone oil, but allylamine is a highly toxic substance and does not meet the requirements for safe production.

[0004] Furthermore, epoxy adhesives typically achieve crosslinking through high-temperature curing, and simply introducing polydimethylsiloxane chains still easily leads to problems such as yellowing. Patent CN201710783001.1 discloses a method for preparing a dialkyl-terminated amino silicone oil, whose side chain structure contains varying numbers of primary and secondary amino groups. However, its main chain lacks heat-resistant groups, and the preparation process is complex, making it unsuitable for direct application to epoxy adhesive structures.

[0005] In summary, existing processes for preparing amino-terminated silicone oils suffer from technical defects such as lengthy reaction procedures, toxic raw material residues, and insufficient temperature resistance of polysiloxane chains. Therefore, the purpose of this invention is to significantly improve the temperature resistance of organosilicon segments by introducing temperature-resistant groups such as phenyl groups into polysiloxane chains. Summary of the Invention

[0006] One of the objectives of this application is to provide an aminophenyl co-modified silicone oil constructed by a ring-opening copolymer of phenylsiloxane and amino dual-terminated compounds, which has both terminal amino reactive sites and phenyl heat-resistant structure. When applied to epoxy adhesives, this aminophenyl co-modified silicone oil can effectively improve the flexibility and heat resistance of epoxy adhesives.

[0007] Another object of the present invention is to provide a method for preparing the above-mentioned aminophenyl co-modified silicone oil.

[0008] Therefore, the first technical solution provided by this invention is: an aminophenyl co-modified silicone oil, wherein the amino-modified methylphenyl silicone oil simultaneously contains phenyl groups and amino groups in its structure; the general structural formula is as follows:

[0009] (R1R2R3SiO 1 / 2 ) a (R4R5SiO) b (R6R7SiO) c (R8R9R 10 SiO 1 / 2 ) d

[0010] in:

[0011] R1, R2, R9 and R 10 It is a hydrogen group or a monovalent hydrocarbon group that does not contain aliphatic unsaturated bonds;

[0012] R3 and R8 are monovalent groups in the structure that have at least one primary or secondary amine structure;

[0013] R4 and R5 are monovalent hydrocarbon groups that do not contain aliphatic unsaturated bonds, and R4 and R5 contain at least one or more phenyl groups;

[0014] R6 and R7 are monovalent hydrocarbon groups that do not contain aliphatic unsaturated bonds;

[0015] The values ​​of a, b, c, and d are as follows: 0 < a ≤ 2; b and c are both integers greater than or equal to 0, and at least one of b and c is not 0; d = 2 - a.

[0016] The second technical solution provided by this invention is a method for preparing aminophenyl co-modified silicone oil as described in the first technical solution, comprising the following steps in sequence:

[0017] 1) Weigh the following components by weight: 2.4-10 parts of aminosiloxane; 36.5-73 parts of phenylsilane or phenylsiloxane; 35.5-50 parts of hydrocarbon silane or hydrocarbon siloxane; 0.8-1 part of quaternary ammonium catalyst; 0-12 parts of deionized water;

[0018] 2) Add the aminosiloxane, phenylsilane or phenylsiloxane, hydrocarbon silane or hydrocarbon siloxane, quaternary ammonium catalyst and deionized water weighed in step 1) to the reactor, and keep it at 80-100℃ for 0.5-1.5h under nitrogen atmosphere;

[0019] 3) Continue heating to 95℃~100℃ and reflux for 3.5-4.5h;

[0020] 4) Stir at 145℃~150℃ for 1~1.5h;

[0021] 5) After filtering the precipitate, the liquid is rotary evaporated to remove low-boiling substances. The resulting product is the aminophenyl co-modified silicone oil temperature resistant agent.

[0022] Furthermore, the preparation method of the above-mentioned aminophenyl co-modified silicone oil includes the following steps in sequence:

[0023] 1) Weigh the following components by weight: 2.4-10 parts of aminosiloxane; 36.5-73 parts of phenylsilane or phenylsiloxane; 35.5-50 parts of hydrocarbon silane or hydrocarbon siloxane; 0.8-1 part of quaternary ammonium catalyst; 0-12 parts of deionized water;

[0024] 2) Add the aminosiloxane, phenylsilane or phenylsiloxane, hydrocarbon silane or hydrocarbon siloxane, quaternary ammonium catalyst and deionized water weighed in step 1) to a straight four-necked flask equipped with a thermometer, condenser and constant pressure funnel, and keep it at 90°C for 1 hour under nitrogen atmosphere.

[0025] 3) Continue heating to 95℃~100℃ and reflux for 4 hours;

[0026] 4) Remove the reflux condenser and open the container, heat to 145℃~150℃ and stir for 1~1.5h;

[0027] 5) Use filter paper or filter membrane to remove scum and sediment from the liquid; then evaporate the liquid at 150℃ and a vacuum of not less than -0.90MPa to remove low-boiling substances. The resulting product is the aminophenyl co-modified silicone oil temperature resistant agent.

[0028] Furthermore, the above-mentioned method for preparing aminophenyl co-modified silicone oil is characterized in that the aminosiloxane is 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(aminoethyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(aminoisobutyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(aminoethylaminopropyl)-1,1,3,3-tetramethyldisiloxane, 1,3- One or more of the following: bis(aminocyclohexyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(benzylaminopropyl)-1,1,3,3-tetramethyldisiloxane, aminopropyl-terminated polydimethylsiloxane, aminoethyl-terminated polydimethylsiloxane, aminoisobutyl-terminated polydimethylsiloxane, aminoethylaminopropyl-terminated polydimethylsiloxane, aminocyclohexyl-terminated polydimethylsiloxane, and benzylaminopropyl-terminated polydimethylsiloxane.

[0029] Furthermore, in the above-mentioned method for preparing aminophenyl co-modified silicone oil, the phenylsilane is one or more of diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane.

[0030] Furthermore, in the above-mentioned method for preparing aminophenyl co-modified silicone oil, the phenylsiloxane is one or more of 2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, pentamethylpentaphenylcyclopentasiloxane, methylphenylsiloxane mixed rings, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, and 1,1,3,5,5-pentamethyl-3-phenyltrisiloxane.

[0031] Furthermore, in the above-mentioned method for preparing aminophenyl co-modified silicone oil, the hydrocarbon silane is one or more of dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dibutyldimethoxysilane, dicyclopentyldimethoxysilane, methylcyclohexyldimethoxysilane, and ethylcyclohexyldimethoxysilane.

[0032] Furthermore, in the above-mentioned method for preparing aminophenyl co-modified silicone oil, the hydrocarbon siloxane is one or more of the following: hydroxyl-terminated polydimethylsilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and a mixture of dimethylcyclosiloxane.

[0033] Furthermore, in the above-mentioned method for preparing aminophenyl co-modified silicone oil, the quaternary ammonium catalyst is one or more of tetramethylammonium hydroxide and its hydrate, tetraethylammonium hydroxide and its hydrate, tetrapropylammonium hydroxide and its hydrate, tetrabutylammonium hydroxide and its hydrate, hexamethyldiammonium hydroxide and its hydrate, benzyltrimethylammonium hydroxide and its hydrate, and 1-adamantyltrimethylammonium hydroxide and its hydrate.

[0034] Another technical solution of the present invention is to provide an adhesive comprising the aminophenyl co-modified silicone oil described in the first technical solution.

[0035] Furthermore, the above-mentioned adhesive comprises the following components in parts by weight: 10 parts epoxy resin; 2 parts aminophenyl co-modified silicone oil; 1.21-1.23 parts dicyandiamide; 0.34-0.40 parts silicone defoamer; and 0.34-0.40 parts silicone leveling agent.

[0036] Beneficial effects

[0037] 1. The technical solution provided by this invention uses a quaternary ammonium catalytic system to achieve the directional ring-opening polymerization of siloxane monomers. During the reaction, the system is stably maintained in the alkaline range, effectively avoiding the generation of side reactions and the use of highly toxic allylamine raw materials. Therefore, it avoids the impact of catalyst or allylamine residues in the hydrosilylation process on product performance.

[0038] 2. The technical solution provided by this invention, which uses amino-terminated phenyl co-modified silicone oil as a temperature-resistant agent, results in a lower pull-out force decay in the modified epoxy adhesive compared to the traditional dicyandiamide curing system. This demonstrates that this invention significantly improves the temperature resistance of epoxy adhesive systems.

[0039] 3. The technical solution provided by this invention enables the epoxy resin to crosslink with the polysiloxane chain during the ring-opening process catalyzed by amine catalysts, embedding the heat-resistant groups into the epoxy resin-organosilicon network, thereby reducing the problem of poor temperature resistance of traditional unit epoxy adhesives.

[0040] 4. The technical solution provided by the present invention constructs a polysiloxane chain with gradient polarity by precisely designing the molar ratio of phenyl and amino groups in the silicone oil structure. This structure can not only form hydrogen bonds with the dicyandiamide curing agent for synergistic effect, but also enhance the interfacial bonding strength with epoxy resin through the π-π stacking effect of phenyl groups. Attached Figure Description

[0041] Figure 1 The FTIR spectra of Examples 1-5 are shown below;

[0042] Figure 2 The images are 1H NMR spectra of Examples 1-4. Detailed Implementation

[0043] The present application will be further described below with reference to embodiments, but this does not constitute any limitation on the present application. Any limited modifications made within the scope of the claims of the present application shall still be within the scope of the claims of the present application.

[0044] Example 1

[0045] 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (19.88 g), octamethylcyclotetrasiloxane (111.97 g), methylphenyl mixed cyclic compound (68.15 g), and tetramethylammonium hydroxide pentahydrate (1.60 g) were added to a straight four-necked flask equipped with a thermometer, condenser, and constant pressure funnel. The mixture was kept at 90°C for 1 h under nitrogen atmosphere; the temperature was then increased to 95°C and refluxed for 4 h; the reflux condenser was removed, the container was opened, and the mixture was heated to 145°C and stirred for 1.5 h; after cooling to room temperature, the liquid was filtered to remove scum and precipitate; then, the liquid was rotary evaporated at 150°C and -0.95 MPa to remove low-boiling-point substances, yielding the target product, aminophenyl co-modified silicone oil, denoted as A1. (Product A1 mass: 169.79 g; yield 84.90%)

[0046] Example 2

[0047] 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (19.88 g), decamethylcyclopentasiloxane (97.97 g), methylphenyl mixed cyclic compound (95.40 g), and tetraethylammonium hydroxide (0.50 g) were added to a straight four-necked flask equipped with a thermometer, condenser, and constant pressure funnel. The mixture was kept at 90°C for 1 hour under nitrogen atmosphere. The temperature was then increased to 95°C–100°C and refluxed for 4 hours. The reflux condenser was then removed, and the container was opened. The mixture was heated to 145°C and stirred for 1.5 hours. After cooling to room temperature, the mixture was filtered to remove scum and precipitate. The liquid was then rotary evaporated at 150°C and -0.96 MPa to remove low-boiling-point substances, yielding the target product, aminophenyl co-modified silicone oil, denoted as A2. (Product A2 mass: 185.32 g; yield 92.66%)

[0048] Example 3

[0049] 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (9.94 g), a mixture of dimethylcyclosiloxanes (108.29 g), methylphenyldimethoxysilane (109.37 g, 0.60 mol), and tetramethylammonium hydroxide (0.94 g) were added to a straight four-necked flask equipped with a thermometer, condenser, and constant pressure funnel. The mixture was kept at 90 °C for 1 h under nitrogen atmosphere. The temperature was then increased to 100 °C and refluxed for 4 h. The reflux condenser was removed, the container was opened, and the mixture was heated to 150 °C and stirred for 1 h. After cooling to room temperature, the mixture was filtered to remove scum and precipitate. The liquid was then rotary evaporated at 150 °C and -0.98 MPa to remove low-boiling-point substances, yielding the target product, aminophenyl co-modified silicone oil, denoted as A3. (Product A3 mass: 171.45 g; yield 85.73%)

[0050] Example 4

[0051] Aminopropyl-terminated polydimethylsiloxane (molecular weight 2000, 53.33 g), octamethylcyclotetrasiloxane (78.53 g), methylphenyl mixed cyclic compound (68.15 g), and tetramethylammonium hydroxide pentahydrate (1.60 g) were added to a straight four-necked flask equipped with a thermometer, condenser, and constant pressure funnel. The mixture was kept at 90°C for 1 hour under nitrogen atmosphere. The temperature was then increased to 95°C–100°C and refluxed for 4 hours. The reflux condenser was then removed, and the container was opened. The mixture was heated to 145°C and stirred for 1.5 hours. After cooling to room temperature, the mixture was filtered to remove scum and precipitate. The liquid was then rotary evaporated at 150°C and -0.95 MPa to remove low-boiling-point substances, yielding the target product, aminophenyl co-modified silicone oil, denoted as A4. (Product A4 mass: 163.57 g; yield 81.79%)

[0052] Example 5

[0053] 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (6.63 g), decamethylcyclopentasiloxane (97.97 g), methylphenyl mixed rings (95.40 g), and tetraethylammonium hydroxide (0.50 g) were added to a straight four-necked flask equipped with a thermometer, condenser, and constant pressure funnel. The mixture was kept at 90°C for 1 hour under nitrogen atmosphere. The temperature was then increased to 95°C–100°C and refluxed for 4 hours. The reflux condenser was then removed, and the container was opened. The mixture was heated to 145°C and stirred for 1.5 hours. After cooling to room temperature, the mixture was filtered to remove scum and precipitate. The liquid was then rotary evaporated at 150°C and -0.96 MPa to remove low-boiling-point substances, yielding the target product, aminophenyl co-modified silicone oil, denoted as A5. (Product A5 mass: 179.36 g; yield 89.68%)

[0054] The test standards for the aminophenyl co-modified silicone oils prepared in Examples 1 to 5 are as follows:

[0055] (1) Fourier transform infrared spectroscopy (FTIR)

[0056] A Nicolet iS50 Fourier transform infrared spectrometer manufactured by Thermo Fisher Scientific, Germany, was used to scan the wavelength range of 4000–600 cm⁻¹ using the KBr pellet method. -1 The resolution is 4cm. -1 The results were obtained from 32 scans.

[0057] (2) Proton NMR spectrum 1 H-NMR)

[0058] The measurements were performed using a Bruker AVANCE III 400MHz Superconducting Fourier nuclear magnetic resonance spectrometer (Swiss), at room temperature, with deuterated chloroform (CDCl3) as the solvent. 1 The amino content of the prepared aminophenyl co-modified silicone oil can be determined by the ¹H NMR internal standard method. The specific method is as follows: At room temperature, using 1,4-dioxane as an internal standard and CDCl3 as a solvent, 0.2 g of the sample prepared in Examples 1-5 and 0.02 g of 1,4-dioxane were weighed and mixed in CDCl3. After sonication for 20 min, the amino content (NH2%) of the silicone oil was measured and calculated.

[0059] The specific calculation method is as follows:

[0060]

[0061] Where: A is the H proton peak area on the β-C atom of the amino group (δ=1.44ppm);

[0062] B represents the H peak area of ​​the –CH2– proton in 1,4-dioxane;

[0063] W i It is the mass (g) of 1,4-dioxane; W s It is the mass of the sample (g).

[0064] 88 is the molar mass of 1,4-dioxane;

[0065] 8 represents the number of H protons in 1,4-dioxane;

[0066] 2 represents the number of H protons on the β-C atom of the amino group.

[0067] (3) Viscosity: At 25℃, a digital rotational viscometer was used, and the torque of the rotating disk was controlled to fluctuate around 50%, and the test was conducted according to GB / T 10247-2008.

[0068] (4) Refractive index: Tested according to GB / T 6488-2008; the refractive index of the liquid was determined by Abbe refractometer at 25℃.

[0069] (5) Density: Tested according to GB / T 6750-2007; the density of the liquid was determined at 25℃ using a density cup.

[0070] (6) Storage stability: According to GB / T 7123.2-2002, the storage period is obtained with viscosity as the indicator, and the storage stability is compared with the length of the storage period.

[0071] Test characterization results:

[0072] 1. Structural characterization

[0073] The FTIR spectra of the aminophenyl co-modified silicone oils described in Examples 1-5 are as follows: Figure 1 As shown. 3072cm -1 The part is a benzene ring sp. 2 Hybrid C-H bond stretching vibration absorption peak; 2960 cm⁻¹ -1 The site is silyl methyl sp 3 Hybrid C-H bond stretching vibration absorption peak; 2890 cm⁻¹ -1 The methylene sp 3 Absorption peak of hybrid C-H bond stretching vibration; 1592 cm⁻¹ -1 The weak, broad peak at 1439 cm⁻¹ is the absorption peak of the bending vibration of the N-H hydrogen atom in amino groups. -1 and 1429cm -1 The locations are silyl methyl sp. 3 Hybridized C—H and methylene sp 3 The bending vibration absorption peak of hybrid C—H; 1257 cm⁻¹ -1 847cm -1 790cm -1 The peak at 1126 cm⁻¹ is a characteristic absorption peak of the Me₂SiO structure. -1 The absorption peak at 1017 cm⁻¹ corresponds to the Si—C stretching vibration absorption peak in the SiCH₂CH₂CH₂NH₂ structure. -1 The peak at this location corresponds to the Si-C stretching vibration absorption peak of the Si-O-Si structure. Figure 1 In the range of 3200-3400cm -1 The absence of broad peaks within the range indicates that there are few residual hydroxyl groups during the reaction process.

[0074] The aminophenyl co-modified silicone oils described in Examples 1-4 1 H NMR spectrum as shown Figure 2 As shown. 1H NMR (400MHz, CDCl3): δ (ppm) = 7.35 ~ 7.57 (d, 5H, -Ph), 2.71 ~ 2.57 (d, 2H, -CH2N-), 2.22 ~ 2.03 (d, 2H, -NH2), 1.44 (s,-CH2CH2CH2-,2H),0.54(m,-CH2CH2CH2-&CH3SiPh,5H),0.30(s,CH3SiCH3,6H),0.07(s,(CH3)2SiCH2-,6H). of embodiment 1 A distinct hydrogen proton peak of -CH2CH2CH2NH2 was observed in all H NMR spectra.

[0075] 2. Physical property characterization

[0076] The physical properties of the amino-terminated phenyl silicone oils described in Examples 1-5 are shown in Table 1.

[0077] Table 1 Physical properties of Examples 1-5

[0078]

[0079] Examples 6-10, Comparative Examples 1-2

[0080] Epoxy resin (bisphenol F type, epoxy equivalent 170 g / eq), aminopropyl-terminated polydimethylsiloxane (molecular weight 2000, Silok3262F from Guangzhou Silok New Materials Co., Ltd.), Examples 1-5, dicyandiamide curing agent and additives were blended according to the proportions shown in Table 2, and then cured at 180°C for 30 min to obtain Examples 6-10 and Comparative Examples 1-2.

[0081] Table 2. Component list of Examples 6-10 and Comparative Examples 1-2

[0082]

[0083] The test standards for Examples 6 to 10 and Comparative Examples 1 to 2 are as follows:

[0084] (1) Pull-out force test: Apply adhesive to the surface of a cylindrical pure copper fixture with a diameter of φ=1.5cm, connect the two fixtures together and cure them, and calculate the pull-out force according to the formula: maximum force / area.

[0085] (2) High and low temperature impact test: The copper sheet coated with cured adhesive was subjected to high and low temperature impact test for 3, 6 and 12 cycles, and then the adhesive pull-out force was tested according to the above standard.

[0086] Pull-out force test and high and low temperature impact test

[0087] Table 3 shows the pull-out force test results of Examples 6-10 and Comparative Examples 1-2 after curing at 180℃ for 30 min and after 3, 6, and 12 high and low temperature impact cycles from -40℃ to 285℃. As can be seen from Table 3, compared with the comparative examples, when using the same type of epoxy resin as the adhesive body, the five aminophenyl co-modified silicone oils provided in Examples 1-5 of this invention as temperature-resistant additives still exhibit high pull-out force after 12 high and low temperature impact cycles from -40℃ to 285℃. Furthermore, with increasing impact cycles, the pull-out force attenuation rate of the modified epoxy adhesive is significantly lower than that of the unmodified adhesive formulation (Comparative Example 1). In addition, Comparative Example 2 uses aminopropyl-terminated polydimethylsiloxane as the temperature-resistant component. The aminopropyl-terminated polydimethylsiloxane side chain does not contain phenyl groups as temperature-resistant groups, resulting in a still relatively high attenuation rate.

[0088] Table 3. Pull-out force test and high / low temperature impact resistance test of Examples 6-10 and Comparative Examples 1-2

[0089]

[0090] The embodiments presented herein are merely selected implementations based on combinations of all possible embodiments. The appended claims should not be limited to the embodiments described herein. Some numerical ranges used in the claims include sub-ranges within them, and variations within these ranges should also be covered by the appended claims.

Claims

1. An aminophenyl co-modified silicone oil, characterized in that, This amino-modified methylphenyl silicone oil contains both phenyl and amino groups in its structure; its general structural formula is as follows: (R1R2R3SiO 1 / 2 ) a (R4R5SiO) b (R6R7SiO) c (R8R9R 10 Not. 1 / 2 ) d in: R1, R2, R9 and R 10 It is a hydrogen group or a monovalent hydrocarbon group that does not contain aliphatic unsaturated bonds; R3 and R8 are monovalent groups in the structure that have at least one primary or secondary amine structure; R4 and R5 are monovalent hydrocarbon groups that do not contain aliphatic unsaturated bonds, and at least one of R4 and R5 contains a phenyl group; R6 and R7 are monovalent hydrocarbon groups that do not contain aliphatic unsaturated bonds; The values ​​of a, b, c, and d are as follows: 0 < a ≤ 2; b and c are both integers greater than or equal to 0, and at least one of b and c is not 0; d = 2 - a.

2. The method for preparing the aminophenyl co-modified silicone oil according to claim 1, characterized in that, The steps are as follows: 1) Weigh the following components by weight: 2.4-10 parts of aminosiloxane; 36.5-73 parts of phenylsilane or phenylsiloxane; 35.5-50 parts of hydrocarbon silane or hydrocarbon siloxane; 0.8-1 part of quaternary ammonium catalyst; 0-12 parts of deionized water; 2) Add the aminosiloxane, phenylsilane or phenylsiloxane, hydrocarbon silane or hydrocarbon siloxane, quaternary ammonium catalyst and deionized water weighed in step 1) to the reactor, and keep it at 80-100℃ for 0.5-1.5h under nitrogen atmosphere; 3) Continue heating to 95℃~100℃ and reflux for 3.5-4.5h; 4) Stir at 145℃~150℃ for 1~1.5h; 5) After filtering the precipitate, the liquid is rotary evaporated to remove low-boiling substances. The resulting product is the aminophenyl co-modified silicone oil temperature resistant agent.

3. The method for preparing aminophenyl co-modified silicone oil according to claim 1, characterized in that, The aminosiloxanes mentioned are 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(aminoethyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(aminoisobutyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(aminoethylaminopropyl)-1,1,3,3-tetramethyldisiloxane, and 1,3-bis(aminocyclohexyl)-1,1,3 One or more of the following: 3-tetramethyldisiloxane, 1,3-bis(benzylaminopropyl)-1,1,3,3-tetramethyldisiloxane, aminopropyl-terminated polydimethylsiloxane, aminoethyl-terminated polydimethylsiloxane, aminoisobutyl-terminated polydimethylsiloxane, aminoethylaminopropyl-terminated polydimethylsiloxane, aminocyclohexyl-terminated polydimethylsiloxane, and benzylaminopropyl-terminated polydimethylsiloxane.

4. The method for preparing aminophenyl co-modified silicone oil according to claim 1, characterized in that, The phenylsilane is one or more of diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane.

5. The method for preparing aminophenyl co-modified silicone oil according to claim 1, characterized in that, The phenylsiloxane is one or more of the following: 2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, pentamethylpentaphenylcyclopentasiloxane, methylphenylsiloxane mixed rings, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, and 1,1,3,5,5-pentamethyl-3-phenyltrisiloxane.

6. The method for preparing aminophenyl co-modified silicone oil according to claim 1, characterized in that, The hydrocarbon silane is one or more of dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dibutyldimethoxysilane, dicyclopentyldimethoxysilane, methylcyclohexyldimethoxysilane, and ethylcyclohexyldimethoxysilane.

7. The method for preparing aminophenyl co-modified silicone oil according to claim 1, characterized in that, The hydrocarbon-based siloxane is one or more of the following: hydroxyl-terminated polydimethylsilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and a mixture of dimethylcyclosiloxane.

8. The method for preparing aminophenyl co-modified silicone oil according to claim 1, characterized in that, The quaternary ammonium catalyst is one or more of the following: tetramethylammonium hydroxide and its hydrate, tetraethylammonium hydroxide and its hydrate, tetrapropylammonium hydroxide and its hydrate, tetrabutylammonium hydroxide and its hydrate, hexamethyldiammonium hydroxide and its hydrate, benzyltrimethylammonium hydroxide and its hydrate, and 1-adamantyltrimethylammonium hydroxide and its hydrate.

9. An adhesive, characterized in that, Includes the aminophenyl co-modified silicone oil as described in claim 1.

10. The adhesive according to claim 1, characterized in that, The product comprises the following components in parts by weight: 10 parts epoxy resin; 2 parts aminophenyl co-modified silicone oil; 1.21-1.23 parts dicyandiamide; 0.34-0.40 parts silicone defoamer; and 0.34-0.40 parts silicone leveling agent.

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