POSS-modified urea derivatives and their preparation methods, epoxy resin compositions

Abstract

This invention relates to the field of organic synthesis, and particularly to POSS-modified urea derivatives, their preparation methods, and epoxy resin compositions. This invention prepares POSS-modified urea derivatives as shown in Formula I by linking a cage-like silsesquioxane (POSS) backbone to a urea of ​​a certain chain length. These derivatives can be used as curing agents for epoxy resins. Using this curing agent allows epoxy resins to cure rapidly at a moderate temperature of around 150°C, with a minimum curing time of approximately 2.5 minutes. Compared to the curing times measured in hours at this temperature in traditional techniques, this significantly improves efficiency. Furthermore, it maintains a gelation time before curing that is not too short, reaching a maximum of 3.2 minutes, allowing sufficient operating time. Simultaneously, the product obtained through such rapid curing also exhibits high performance, including high impact strength, high flexural modulus, and good thermal stability.

Description

[0001] This application is a divisional application of Chinese Patent Application No. CN202111665206.2, filed on December 30, 2021, entitled "POSS-modified urea derivatives and their preparation methods, epoxy resin compositions", the entire contents of which are incorporated herein by reference. Technical Field

[0002] This invention relates to the field of organic synthesis, and in particular to POSS-modified urea derivatives and their preparation methods, as well as epoxy resin compositions. Background Technology

[0003] Epoxy resin cured products possess excellent adhesive strength and resistance to high and low temperatures, along with good dielectric properties and ease of processing, making them widely used in aerospace, construction, and machinery industries. However, epoxy resins exhibit incomplete reaction and prolonged curing times when cured at medium temperatures (around 150°C). Artificially accelerating the curing rate at medium temperatures results in brittle cured products with low impact strength, necessitating toughening modifications. Traditional techniques typically involve adding toughening agents such as polyamides, polyetheramines, polyurethanes, or rubber to improve the toughness of cured epoxy resins, but this also reduces the material's flexural modulus and heat resistance. Summary of the Invention

[0004] Therefore, it is necessary to provide a POSS-modified urea derivative and its preparation method. This derivative can be used as a curing agent for epoxy resin, enabling the epoxy resin to cure rapidly under medium temperature conditions. The cured product has the advantages of high impact strength, high flexural modulus, and good heat resistance.

[0005] One aspect of the present invention provides a POSS-modified urea derivative having the structure shown in Formula I:

[0006]

[0007] In this case, each occurrence of X is independently selected from -(CR). 4 R 5 ) n -or phenylene;

[0008] Each time n appears, it is independently selected from 1, 2, 3, 4, 5, or 6;

[0009] R 2 ~R 5 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, methyl, methoxy, or ethyl;

[0010] * indicates a connection point.

[0011] In some embodiments, the POSS-modified urea derivatives have the structure shown in Formula II:

[0012]

[0013] In this case, each occurrence of X is independently selected from -(CR). 4 R 5 ) n -or 1,4-phenylene;

[0014] Each time n appears, it is independently selected from 1, 2, 3, 4, 5, or 6;

[0015] R 2 R 4 R 5 Each occurrence is independently selected from -H, methyl, or ethyl;

[0016] * indicates a connection point.

[0017] In another aspect, the present invention provides a method for preparing the aforementioned POSS-modified urea derivatives, comprising the following steps:

[0018] The POSS-modified urea derivatives were prepared by reacting the compounds shown in Formula III and Formula IV with carbonyl diimidazole under nitrogen or argon protection at 20°C to 35°C.

[0019]

[0020] In another aspect, the present invention provides an epoxy resin composition comprising, by weight, the following components:

[0021] 100 parts epoxy resin

[0022] 5-53 parts of POSS-modified urea derivatives

[0023] 0-150 parts of filler and solvent;

[0024] Wherein, the POSS-modified urea derivative is the aforementioned POSS-modified urea derivative.

[0025] In some embodiments, the epoxy resin is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, linear phenolic epoxy resin, cresol phenolic epoxy resin, bisphenol A phenolic epoxy resin, tetramethylbisphenol F type epoxy resin, bisphenol M type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol P type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol phenolic epoxy resin, anthracene type epoxy resin, phenol The epoxy resins include one or more of the following: phthaloyl epoxy resin, phenoxy epoxy resin, norbornene epoxy resin, adamantane epoxy resin, fluorene epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, dicyclopentadiene phenolic epoxy resin, aralkyl epoxy resin, aralkylphenolic epoxy resin, epoxy resin containing an aryl ether structure, alicyclic epoxy resin, polyol epoxy resin, silicone epoxy resin, nitrogen-containing epoxy resin, phosphorus-containing epoxy resin, glycidylamine epoxy resin, and glycidyl ester epoxy resin.

[0026] In some embodiments, the filler is selected from one or more of the following: silica, quartz glass powder, mica powder, hollow glass microspheres, microcrystalline glass, nepheline, titanium dioxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, talc, alumina, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, nepheline, clay, kaolin, composite silica powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, and Q glass powder.

[0027] The present invention also provides an epoxy resin coating, which is cured from the epoxy resin composition of any of the foregoing embodiments.

[0028] The present invention also provides a prepreg comprising a reinforcement and an epoxy resin composition of any of the foregoing embodiments attached to the surface of the reinforcement; or comprising a reinforcement and the foregoing epoxy resin coating disposed on the surface of the reinforcement.

[0029] In some embodiments, the reinforcement is made from one or more of plant fibers, animal fibers, mineral fibers, and synthetic fibers.

[0030] The present invention also provides a laminate comprising one or more sheets of prepreg as described in any of the foregoing embodiments.

[0031] The present invention also provides a metal foil-coated laminate, which includes the aforementioned laminate and metal foil disposed on one or both sides of the laminate.

[0032] The present invention also provides a printed circuit board comprising the aforementioned laminate and / or the aforementioned metal foil laminate.

[0033] By linking a cage-like silsesquioxane (POSS) backbone to a urea of ​​a certain chain length, a POSS-modified urea derivative as shown in Formula I is prepared. This derivative can be used as a curing agent for epoxy resins, enabling the epoxy resins to cure rapidly at a moderate temperature of around 150°C, with a minimum curing time of approximately 2.5 minutes. Compared to the curing time measured in hours at this temperature in traditional technologies, this significantly improves efficiency. Furthermore, it maintains a gelation time before curing that is not too short, reaching a maximum of 3.2 minutes, allowing sufficient operating time. Simultaneously, the product obtained through such rapid curing also exhibits high performance, including high impact strength, high flexural modulus, and good thermal stability. Detailed Implementation

[0034] To facilitate understanding of the present invention, a more complete description will be given below with reference to relevant embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention.

[0035] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of the invention, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified. In the description of the present invention, "several" means at least one, such as one, two, etc., unless otherwise explicitly specified.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0037] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0038] In this invention, numerical ranges are involved. Unless otherwise specified, the numerical ranges are considered continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe features or characteristics, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0039] Unless otherwise specified, the percentage content involved in this invention refers to mass percentage for solid-liquid mixtures and solid-phase-solid mixtures, and volume percentage for liquid-phase-liquid mixtures.

[0040] Unless otherwise specified, all percentage concentrations mentioned in this invention refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.

[0041] Unless otherwise specified, the temperature parameters in this invention can be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows temperature fluctuations within the precision range controlled by the instrument.

[0042] One aspect of the present invention provides a POSS-modified urea derivative having the structure shown in Formula I:

[0043]

[0044] In this case, each occurrence of X is independently selected from -(CR). 4 R 5 ) n -or phenylene;

[0045] Each time n appears, it is independently selected from 1, 2, 3, 4, 5, or 6;

[0046] R 2 ~R 5 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, methyl, methoxy, or ethyl;

[0047] * indicates a connection point.

[0048] Cage-type polysilsesquioxane (POSS) is a high-performance organic-inorganic hybrid material. It uses POSS as the inorganic component and organic substituents attached to silicon atoms as the organic component. The inorganic and organic phases are strongly bonded together, avoiding the problems of inorganic particle aggregation and weak interfacial bonding. This makes it a high-performance hybrid material that can be easily composited with polymer matrices through copolymerization, grafting, or blending to improve the temperature resistance, flame retardancy, and toughening properties of the polymer matrix. Based on this, to address the problem of high brittleness and low impact strength of epoxy resins after rapid curing at moderate temperatures (around 150°C) in traditional technologies, researchers have attempted to introduce the POSS skeleton into epoxy resin curing agents. For example, combining the POSS skeleton with amino groups can improve the performance of epoxy resins cured at moderate temperatures using amine curing agents. While this method allows the cured epoxy resin to possess both good toughness and high flexural modulus, the curing time at moderate temperatures remains relatively long (around half an hour) without excessively sacrificing the cured product's performance, offering limited improvement to the curing speed.

[0049] Through extensive research, the inventors of this invention discovered that combining POSS with ureas of a certain chain length yields POSS-modified urea derivatives as shown in Formula I. These derivatives can serve as epoxy resin curing agents, enabling epoxy resins to cure rapidly at a moderate temperature of around 150°C, with a minimum curing time of approximately 2.5 minutes. This significantly improves efficiency compared to the hourly curing times at this temperature in traditional techniques. Furthermore, it maintains a gelation time before curing that is not too short, reaching a maximum of 3.2 minutes, allowing sufficient processing time. Simultaneously, the product obtained through such rapid curing also exhibits high performance, including high impact strength, high flexural modulus, and good thermal stability.

[0050] In the POSS-modified urea derivative structure shown in Formula I, the main chain has a certain length and contains no branches or only short branches (methyl, methoxy, ethyl), which makes the steric hindrance around the reactive urea groups small, allowing for better reaction with epoxy resin. It can achieve a high crosslinking density in a short time, enabling the epoxy resin to cure rapidly under medium temperature conditions, and the cured epoxy resin has high impact strength. At the same time, the rigidity of the structure will not decrease due to excessive main chain length, thus affecting the flexural modulus of the cured epoxy resin.

[0051] In some embodiments, the POSS-modified urea derivatives have the structure shown in Formula II:

[0052]

[0053] In this case, each occurrence of X is independently selected from -(CR). 4 R 5) n -or 1,4-phenylene;

[0054] Each time n appears, it is independently selected from 1, 2, 3, 4, 5, or 6;

[0055] R 2 R 4 R 5 Each occurrence is independently selected from -H, methyl, or ethyl;

[0056] * indicates a connection point.

[0057] In another aspect, the present invention provides a method for preparing the aforementioned POSS-modified urea derivatives, comprising the following steps:

[0058] The POSS-modified urea derivatives were prepared by reacting the compounds shown in Formula III and Formula IV with carbonyl diimidazole under nitrogen or argon protection at 20°C to 35°C.

[0059]

[0060] In some implementations, the following steps are included:

[0061] The compound shown in Formula III, triethylamine, and solvent are mixed to prepare a solution. Under nitrogen or argon protection and at 20°C to 35°C, carbonyl diimidazole (CDI) is added to the solution and stirred for 0.5 h to 1.5 h. Then, the solution of the compound shown in Formula IV is added and stirring is continued for 9 h to 11 h. The reaction system is then poured into water, extracted with an organic solvent, and washed, dried, concentrated, separated, and purified.

[0062] Preferably, the compound shown in Formula III, triethylamine, and solvent are mixed to prepare a solution; under nitrogen or argon protection and at 25°C, carbonyl diimidazole (CDI) is added to the aforementioned solution, and after stirring for 1 hour, a solution of the compound shown in Formula IV is added, and stirring is continued for 10 hours. Then, the reaction system is poured into water, extracted with an organic solvent, and then washed, dried, concentrated, separated, and purified.

[0063] In some embodiments, the molar ratio of the compound represented by Formula III, triethylamine, CDI, and the compound represented by Formula IV is 1:(8-10):(8-10):(8-10), preferably 1:8:8:8.1.

[0064] In some embodiments, anhydrous tetrahydrofuran is used to dissolve the compound represented by Formula III and triethylamine.

[0065] In some embodiments, N,N-dimethylformamide is used as a compound represented by formula IV.

[0066] In some implementations, dichloromethane is used for extraction.

[0067] In another aspect, the present invention provides an epoxy resin composition comprising, by weight, the following components:

[0068] 100 parts epoxy resin

[0069] 5-53 parts of POSS-modified urea derivatives

[0070] 0-150 parts of filler and solvent;

[0071] Among them, the POSS-modified urea derivatives are the POSS-modified urea derivatives shown in Formula I or Formula II above.

[0072] The epoxy resin composition composed of POSS-modified urea derivatives and epoxy resin shown in Formula I has a long gelation time at a moderate temperature of around 150°C, allowing for more workable time; it also has a fast curing speed and good cured product properties.

[0073] In some embodiments, the amount of POSS-modified urea derivative in the epoxy resin composition may be, for example, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, or 50 parts. The amount of POSS-modified urea derivative in the epoxy resin composition directly affects the degree of reaction between the two, thus influencing the rate of gelation and curing of the epoxy resin, as well as the properties of the cured product. Controlling its amount within a reasonable range allows for a better balance between gelation and curing rates, and between conflicting properties such as impact strength and flexural modulus.

[0074] In some embodiments, the amount of filler in the epoxy resin composition may be, for example, 25 parts, 50 parts, 75 parts, 100 parts, or 125 parts.

[0075] In some embodiments, N,N-dimethylformamide is used as the solvent.

[0076] In some embodiments, the epoxy resin is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, linear phenolic epoxy resin, cresol phenolic epoxy resin, bisphenol A phenolic epoxy resin, tetramethylbisphenol F type epoxy resin, bisphenol M type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol P type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol phenolic epoxy resin, anthracene type epoxy resin, and phenolphthalein. The epoxy resins include one or more of the following: phenoxy epoxy resins, norbornene epoxy resins, adamantane epoxy resins, fluorene epoxy resins, biphenyl epoxy resins, dicyclopentadiene epoxy resins, dicyclopentadiene phenolic epoxy resins, aralkyl epoxy resins, aralkylphenolic epoxy resins, epoxy resins containing aryl ether structures in their molecules, alicyclic epoxy resins, polyol epoxy resins, silicone epoxy resins, nitrogen-containing epoxy resins, phosphorus-containing epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins.

[0077] In some embodiments, the filler is selected from one or more of the following: silica, quartz glass powder, mica powder, hollow glass microspheres, microcrystalline glass, nepheline, titanium dioxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, talc, alumina, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, nepheline, clay, kaolin, composite silica powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, and Q glass powder.

[0078] It is understood that, without impairing the original properties of the resin composition, the epoxy resin composition may also include additives commonly used in the art, such as one or more of other thermosetting resins, thermoplastic resins, curing agents, curing accelerators, toughening agents, flame retardants, coupling agents, and defoamers.

[0079] The present invention also provides an epoxy resin coating, which is cured from the epoxy resin composition of any of the foregoing embodiments.

[0080] The present invention also provides a prepreg comprising a reinforcement and an epoxy resin composition of any of the foregoing embodiments attached to the surface of the reinforcement; or comprising a reinforcement and the aforementioned epoxy resin coating disposed on the surface of the reinforcement.

[0081] In some embodiments, the reinforcement is made from one or more of plant fibers, animal fibers, mineral fibers, and synthetic fibers.

[0082] In some embodiments, the reinforcement may be one or more of wood pulp paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving.

[0083] The present invention also provides a laminate comprising one or more sheets of prepreg of any of the foregoing embodiments.

[0084] The present invention also provides a method for preparing the aforementioned laminate, comprising the following steps:

[0085] The sheet-like reinforcement is impregnated in an epoxy resin composition, then removed and dried at 145℃~155℃ for 2min~5min to obtain a laminate raw material layer; if a multilayer laminate is to be prepared, multiple laminate raw material layers are stacked.

[0086] The present invention also provides a metal foil-coated laminate, which includes the aforementioned laminate and metal foil disposed on one or both sides of the laminate.

[0087] In some embodiments, the metal foil is copper foil, and more specifically, electrolytic copper foil.

[0088] The present invention also provides a method for preparing the aforementioned metal foil-coated laminate, comprising the following steps:

[0089] Metal foil is covered on one or both sides of the laminate, and then processed in a vacuum hot press.

[0090] In some implementations, the processing conditions in the vacuum hot press are as follows:

[0091] Temperature 150℃, vacuum degree 10mBar~20mBar, pressure 20kg / cm 2 Time: 10 minutes.

[0092] The present invention also provides a printed circuit board comprising the aforementioned laminate and / or the aforementioned metal foil laminate.

[0093] The present invention will be further described in detail below with reference to specific embodiments and comparative examples. Experimental parameters not specified in the following specific embodiments should first be referred to the guidelines given in this application, and may also be referred to experimental manuals or other experimental methods known in the art, or the experimental conditions recommended by the manufacturer. It is understood that the instruments and materials used in the following embodiments are relatively specific, and may not be limited to these in other specific embodiments.

[0094] Raw material source:

[0095] POSS (8-p-aminophenyl): Xi'an Qiyue Biotechnology Co., Ltd.

[0096] 8-aminopropyl POSS: Xi'an Qiyue Biotechnology Co., Ltd.;

[0097] Bisphenol A type epoxy resin: NPEL-128, Nan Ya Plastics Industrial Co., Ltd.;

[0098] o-Cresol-formaldehyde epoxy resin: NPCN-704, Nan Ya Plastics Industrial Co., Ltd.;

[0099] Dicyandiamide: Dicy, Ningxia Darong Industrial Group Co., Ltd.;

[0100] Organic urea accelerator UR500: DYHARD UR500, Evonik Industries AG, Germany;

[0101] Silica: SilverBond 706, Siliconware Precision Industries (Shanghai) Co., Ltd.

[0102] POSS-A(X = 1,4-phenylene, R) 2 ~R 3 Preparation of (all H)

[0103] At room temperature, 1 mol of octaaminophenyl POSS, 8 mol of triethylamine (Et3N), and anhydrous tetrahydrofuran (THF) were added to a container and mixed to form a solution. Under a N2 atmosphere, 8 mol of carbonyl diimidazole (CDI) was added to the solution and stirred at a constant temperature for 1 hour. Then, 8.1 mol of aniline in N,N-dimethylformamide (DMF) solution was added, and the mixture was stirred for another 10 hours. The reaction mixture was then poured into water, extracted with dichloromethane, and the organic phase was washed with saturated brine. The phase was then dried with anhydrous Na2SO4 and filtered. The filtrate was concentrated to obtain a crude product, which was separated by column chromatography to obtain a POSS-modified urea derivative product, denoted as POSS-A.

[0104] POSS-B(X=-CH2CH2CH2-,R 2 ~R 3 Preparation of (all H)

[0105] The preparation method is the same as that of POSS-A, except that octa-aminophenyl POSS is replaced with an equal amount of octa-aminopropyl POSS.

[0106] Example 1

[0107] Add 100 parts of bisphenol A type epoxy resin, 25 parts of POSS-A, 50 parts of silica, and an appropriate amount of N,N-dimethylformamide (DMF) to a container and stir evenly to obtain a resin composition containing POSS-modified urea derivatives.

[0108] A sheet of 2116 type fiberglass cloth was impregnated with the resin composition and dried in an oven at 150°C for 3 minutes to obtain a prepreg with a thickness of 0.1 mm. Four sheets of prepreg were combined into a laminate, and an electrolytic copper foil with a thickness of 18 μm was placed on each side of the laminate. The laminate was then placed in a hot press at 150°C, a vacuum was drawn and maintained at a vacuum level of 10 mBar to 20 mBar, and the pressure was increased to 20 kg / cm². 2 After being kept at constant temperature and pressure for 10 minutes, the temperature was lowered to below 40°C. After releasing the pressure and vacuum, the material was removed to obtain a copper-clad laminate with a thickness of 0.4 mm. The copper surface of the copper-clad laminate was completely removed to obtain the laminate.

[0109] In addition, the resin composition is poured into a mold coated with epoxy resin release agent and preheated to 150°C, a vacuum is drawn and maintained at a vacuum level of 10 mBar to 20 mBar, and the pressure is increased to 20 kg / cm². 2 After being kept at constant temperature and pressure for 10 minutes, the temperature was lowered to below 40°C. The pressure was released and the vacuum was released before the material was taken out to obtain an epoxy resin casting for preparing impact strength test specimens.

[0110] The preparation methods of the laminates and epoxy resin castings in the remaining embodiments and comparative examples are the same as those in Example 1. The formulations of the resin compositions in each embodiment and comparative example are shown in Table 1 (the units of each component are parts by mass):

[0111] Table 1

[0112]

[0113] The laminates and epoxy resin castings prepared in each embodiment and comparative example were subjected to performance tests. The test standards are as follows, and the test results are shown in Table 2:

[0114] (1) Tg / ℃ (glass transition temperature): Differential scanning calorimetry (DSC) was performed according to IPC TM-6502.4.25D standard, and samples were prepared using laminates.

[0115] (2) Td / ℃ (thermal decomposition temperature): According to the thermogravimetric analysis (TGA), the test was performed in accordance with the IPC TM-6502.4.24.6 standard, and the sample was prepared using a laminate.

[0116] (3) Impact strength / (kJ / m 2 The test was conducted in accordance with GB / T 1843-2008 standard, using epoxy resin castings for sample preparation, and testing the cantilever beam impact strength of notched specimens at room temperature.

[0117] (4) Bending modulus / GPa: The test was conducted in accordance with ASTM D882 standard. The specimen was prepared using laminate with a thickness of 0.8 mm. The bending strength of the specimen was tested at room temperature.

[0118] (5) Initial reaction temperature / °C: The test was conducted in accordance with GB / T 22232-2008 standard, and the test result is “3.5 extrapolated initial temperature” in the standard.

[0119] (6) Gelation time at 150℃ / sec: The test temperature was changed from 180℃ to 150℃, in accordance with GB / T 16995-1997 standard.

[0120] (7) Curing time / min: Each sample was obtained by impregnating a sheet of 2116 fiberglass cloth with the resin composition provided in each example and comparative example, and drying it in an oven at 200℃ for X sec. The reaction enthalpy of the sample was tested by differential scanning calorimetry (DSC) according to ISO 11357-5-2013. The enthalpy of the reaction was considered to be less than 2J / g in the range of 50℃ to 250℃, and the curing time was recorded as X sec.

[0121] Table 2

[0122] Group Tg Td Impact resistance Flexural modulus Initial reaction temperature gelation time at 150℃ Curing time Example 1 145 358 25 22.0 147 153 160 Example 2 136 349 21 19.2 153 188 220 Example 3 151 364 28 23.5 143 136 150 Example 4 148 368 24 23.8 148 158 160 Example 5 138 350 26 21.6 153 190 230 Example 6 152 345 22 19.0 146 140 150 Example 7 178 357 29 23.1 150 168 180 Comparative Example 1 126 335 15 15.3 165 254 480 Comparative Example 2 141 368 29 18.7 141 117 130 Comparative Example 3 121 323 12 13.8 168 287 1080 Comparative Example 4 124 328 9 15.2 141 152 180 Comparative Example 5 142 348 18 19.6 168 562 1500

[0123] As shown in Tables 1 and 2, when urea derivatives with a POSS structure are selected and used in combination with epoxy resin within the preset dosage range of this invention, a resin composition with excellent performance can be obtained. This resin composition exhibits superior performance compared to similar medium-temperature rapid-curing epoxy resin compositions. Specifically, the Tg (glass transition temperature) of its laminates is greater than 140°C, the Td (thermal decomposition temperature) is greater than 346°C, the flexural modulus is greater than 19 GPa, and the impact strength of the resin casting is greater than 18 kJ / m. 2 .

[0124] In Comparative Example 1, the amount of POSS-B added was less than the preset lower limit of the resin composition, resulting in limited improvement in the performance of the cured product. Tg, Td, impact strength, and flexural modulus were all low, and rapid curing at medium temperature could not be achieved. In Comparative Example 2, the amount of POSS-B added was greater than the upper limit of the resin composition, leading to a decrease in Tg and flexural modulus, and an excessively fast gel time at 150°C, which was detrimental to operation and construction. Comparative Example 3 showed that the resin composition without POSS-B exhibited the worst performance in all aspects. A comparison between Comparative Example 4 and Example 5 showed that... Although the resin composition can also achieve medium-temperature rapid curing when replacing POSS-B with an organic urea accelerator, its Tg, Td, impact strength, and flexural modulus are all low, failing to achieve the performance provided in the examples. Comparing Comparative Example 5 with Example 4, it can be seen that when using an equal amount of octaaminopropyl POSS to replace POSS-B, the Tg, Td, impact strength, and flexural modulus of the laminate are acceptable, but the initial reaction temperature of its resin composition is too high, the gelation time at 150°C is too long, and the curing time is too long, making it unsuitable for medium-temperature rapid curing scenarios.

[0125] In summary, the POSS-modified urea derivatives provided by this invention can be used as resin compositions for medium-temperature rapid curing, which can reduce the reaction temperature and shorten the curing time. At the same time, the cured products have excellent heat resistance, flexural modulus, toughness and impact strength, and are more tough than general medium-temperature curing agents, and have better heat resistance and flexural modulus than general toughening agents.

[0126] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0127] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. An epoxy resin composition, characterized in that, By weight, it consists of the following components: 100 parts epoxy resin 25-53 parts of POSS-modified urea derivatives 25-75 parts of filler and solvent; The POSS-modified urea derivatives have the structure shown in Formula I: In this case, each occurrence of X is independently selected from -(CR). 4 R 5 ) n -or phenylene; Each time n appears, it is independently selected from 1, 2, 3, 4, 5, or 6; R 2 ~R 5 Each occurrence is independently selected from either -H or -D; * indicates a connection point.

2. The epoxy resin composition according to claim 1, characterized in that, The POSS-modified urea derivatives have the structure shown in Formula II: In each instance, X is independently selected from -CH2CH2CH2- or 1,4-phenylene; R 2 -H; * indicates a connection point.

3. The epoxy resin composition according to claim 1 or 2, characterized in that, The epoxy resin is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, linear phenolic epoxy resin, cresol phenolic epoxy resin, bisphenol A phenolic epoxy resin, tetramethylbisphenol F type epoxy resin, bisphenol M type epoxy resin, bisphenol E type epoxy resin, bisphenol P type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol type epoxy resin, naphthol phenolic epoxy resin, anthracene type epoxy resin, phenolphthalein type epoxy resin, and phenoxy... The following are included in the following categories: basic epoxy resin, norbornene epoxy resin, adamantane epoxy resin, fluorene epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, dicyclopentadiene phenolic epoxy resin, aralkyl epoxy resin, aralkylphenolic epoxy resin, epoxy resin containing aryl ether structure in the molecule, alicyclic epoxy resin, polyol epoxy resin, silicone epoxy resin, nitrogen epoxy resin, phosphorus epoxy resin, glycidylamine epoxy resin, and glycidyl ester epoxy resin; The filler is selected from one or more of the following: silica, quartz glass powder, mica powder, hollow glass microspheres, microcrystalline glass, nepheline, titanium dioxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, talc, alumina, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, zirconium vanadate, zirconium tungstate, hafnium tungstate, clay, kaolin, composite silica powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, and Q glass powder. The solvent is selected from N,N-dimethylformamide; The epoxy resin composition comprises 30 to 53 parts by weight of a POSS-modified urea derivative.

4. The epoxy resin composition according to claim 2, characterized in that, By weight, it includes 45 to 53 parts of POSS-modified urea derivatives; The epoxy resin composition is selected from the composition of (1) or (2): (1) 100 parts of bisphenol A type epoxy resin, 50 parts of POSS-A, 50 parts of silica and N,N-dimethylformamide; wherein POSS-A has the structure shown in Formula II, wherein X is 1,4-phenylene; (2) 100 parts of bisphenol A type epoxy resin, 50 parts of POSS-B, 50 parts of silica and N,N-dimethylformamide; wherein POSS-B has the structure shown in Formula II, wherein X is -CH2CH2CH2-.

5. An epoxy resin coating, characterized in that, It is formed by curing the epoxy resin composition according to any one of claims 1 to 4.

6. A prepreg, characterized in that, The epoxy resin composition according to any one of claims 1 to 4 includes a reinforcing body and an epoxy resin composition attached to the surface of the reinforcing body.

7. The prepreg according to claim 6, characterized in that, The reinforcement is made from one or more of plant fibers, animal fibers, mineral fibers, and synthetic fibers.

8. A laminate, characterized in that, Includes one or more sheet-like prepregs as described in claim 6 or 7.

9. A metal foil-coated laminate, characterized in that, It includes the laminate as described in claim 8 and the metal foil disposed on one or both sides of the laminate.

10. A printed circuit board, characterized in that, Includes the laminate of claim 8 or the metal foil-coated laminate of claim 9.

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