A silicone-modified epoxy resin and its use as a coating agent

Abstract

The application provides a kind of organic silicon compound containing imide bond, the organic silicon compound containing imide bond has as shown in formula (I), formula (II) or formula (III) structure.The organic silicon compound containing imide bond designed by the application can be obtained only by condensation reaction and other steps, which is used as the fatty amine curing agent of epoxy resin and the epoxy resin diluent with adjustable functionality, and then a high toughness and high temperature resistant epoxy resin is obtained.The various epoxy resin curing agents and epoxy resin diluents containing organic silicon and containing imide bond provided by the application are convenient in synthesis method, the types of synthesized epoxy resin are rich, and the organic silicon modified epoxy resin prepared by the application is adjustable in viscosity, excellent in mechanical property, high in temperature resistance grade, and suitable for metal soft magnetic composite insulation coating and other working scenarios.

Description

Technical Field

[0001] This invention belongs to the technical field of coating agents for soft magnetic metal composite materials, and relates to an organosilicon compound containing an imide bond, its application in organosilicon-modified epoxy resin, organosilicon-modified epoxy resin, and its application in the field of coating agents, especially an organosilicon-modified epoxy resin and its application as a coating agent. Background Technology

[0002] Epoxy resins, due to their excellent bonding and mechanical properties, are suitable for the insulating coating process of soft magnetic metal composites. However, conventional epoxy resins suffer from poor toughness and poor resistance to high and low temperatures, which limits the time and temperature of heat treatment processes for soft magnetic metal composites, thus affecting the mechanical strength, effective permeability, and magnetic loss of the composites. Organosilicon-modified epoxy resins are one of the main research directions in the industry. To date, research on organosilicon-modified epoxy resins mainly includes blending modification and copolymerization modification. Blending modification involves physically mixing organosilicon materials with epoxy resins, but poor compatibility leads to uneven material properties. Copolymerization modification utilizes the reaction of active organosilicon with the active groups in epoxy resin components to improve the heat resistance of epoxy resins. Existing technologies have also disclosed some corresponding research schemes, such as patent CN 109385241, which discloses a method for preparing a silicon-grafted epoxy resin adhesive by hydrosilylation reaction under Karstedt catalyst conditions. Patent CN101328301 discloses a multi-component blended modified epoxy resin. The weight percentages of each component are: 30-80% epoxy resin, 2-25% curing agent, 20-80% filler, 0.001-5% thixotropic agent, 0.001-5% viscosity reducer / dispersant, 0-5% defoamer, and 0.5% catalyst (not exceeding the total weight of the epoxy resin and curing agent). The mixture is stirred until homogeneous. (Journal: European Polymer) Journal 43 (2007) 1470–1479 reports a 1,3-bis[3-(4,5-epoxy-1,2,3,6-tetrahydrophthalimide epoxide] prepared from 1,3-bis(3-aminopropyl)tetramethyldisiloxane and tetrahydrophthalic anhydride, and an organosilicon epoxy resin used in conjunction with an anhydride curing agent. Also, “Study on the Synthesis of Polysiloxane-Modified Epoxy Resins,” Zhang Yaguang, China Excellent Master's Thesis Database, B016-109 A hydrosilylation method was disclosed, which uses terminal hydrogen silicone oil and epoxy resin to copolymerize and obtain epoxy resin with a siloxane structure. However, most of the existing methods for modifying organosilicon epoxy resins use hydrosilylation, ammonolysis, chain extension, and other methods to react organosilicon hydrogen bonds, halogenated silanes, and amino silanes to obtain organosilicon compounds that can react with epoxy resin, thereby improving the heat resistance and toughness of epoxy resin. However, long-chain siloxane segments will lower the glass transition temperature of epoxy resin, thus reducing the service temperature.Moreover, taking CN 109385241 as an example, it represents a method for preparing organosilicon epoxy resin by hydrosilylation reaction. However, this method requires the use of Karstedt catalyst, which is a complex of the precious metal Pt. It is expensive and also poses the problem of heavy metal pollution to the environment. The epoxy resin reported in the journal European Polymer Journal 43 (2007) 1470–1479 has a simple structure, which is not conducive to adjusting the epoxy value of the epoxy resin. In addition, its glass transition temperature is lower than 130℃, which cannot meet the process requirements of soft magnetic composite materials for epoxy resin.

[0003] Therefore, finding a more suitable high-performance silicone-modified epoxy resin for soft magnetic composite material coating and bonding processes, overcoming the above-mentioned shortcomings, and using a silicone-modified epoxy resin that is inexpensive, environmentally friendly, easy to prepare, and has high and low temperature resistance as a coating agent is of great significance and is also one of the issues that many forward-looking researchers in the industry are widely concerned about. Summary of the Invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide an organosilicon compound containing an imide bond, its application in organosilicon-modified epoxy resin, the application of organosilicon-modified epoxy resin in the field of coating agents, and particularly an organosilicon-modified epoxy resin coating agent. The organosilicon-modified epoxy resin prepared by the present invention has adjustable viscosity, excellent mechanical properties, and high temperature resistance, making it more suitable for working scenarios such as insulating coating of soft magnetic metal composite materials. Moreover, the preparation method is simple, highly controllable, requires no precious metal catalyst, is environmentally friendly, and inexpensive, making it more suitable for industrial production and application.

[0005] This invention provides an organosilicon compound containing an imide bond, wherein the organosilicon compound containing the imide bond has a structure as shown in formula (I), formula (II) or formula (III):

[0006]

[0007]

[0008] Among them, equation (I) Selected from

[0009] In equations (II) and (III) Each independently selected

[0010] In equations (I), (II), and (III), n represents the degree of polymerization.

[0011] Preferably, n is 3 to 10;

[0012] The compounds with the structures shown in formula (I) and / or formula (II) are aliphatic amine curing agents containing imide bonds and organosilicon structures;

[0013] The compounds with structures shown in formula (II) and / or formula (III) are epoxy resin diluents with adjustable functionality containing imide bonds and organosilicon structures.

[0014] Preferably, the compound with the structure shown in formula (I) is prepared by a condensation reaction of an aromatic dianhydride monomer and a diamine monomer containing a siloxane segment;

[0015] The compound with the structure shown in formula (II) is prepared by a condensation reaction and an epoxidation reaction between a dianhydride monomer containing an unsaturated double bond and a diamine monomer containing a siloxane segment.

[0016] The compound with the structure shown in formula (III) is prepared by condensation reaction, substitution reaction and epoxidation reaction of a dianhydride monomer containing an unsaturated double bond and a diamine monomer containing a siloxane segment.

[0017] Preferably, the aromatic dianhydride monomer includes one or more of PMDA, BPDA, α-BPDA, DSDA, 6FDA, ODPA, BTDA, and 3,3'-HQDPA;

[0018] The diamine monomer containing siloxane segments includes one or more of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, aminopropyl-terminated polydimethylsiloxane, and YASI series polydimethylsiloxane diamine monomers.

[0019] The dianhydride monomer containing unsaturated double bonds includes one or more of norbornene, 2,3-cyclohexenedian anhydride, and 3,4-cyclohexenedian anhydride.

[0020] This invention provides the application of organosilicon compounds containing imide bonds, as described in any one of the above technical solutions, in organosilicon-modified epoxy resins.

[0021] Preferably, the application includes the use of compounds with the structures shown in formula (I) and / or formula (II) as curing agents;

[0022] The mass ratio of the curing agent to the base epoxy resin is (10-120):100;

[0023] The applications include the use of compounds with the structures shown in formula (II) and / or formula (III) as diluents;

[0024] The epoxy resin includes one or more of the following: bisphenol A type, bisphenol F type, bisphenol S type, hydrogenated bisphenol A type, phenolic epoxy resin, aliphatic epoxy resin, glycidylamine type epoxy resin, and hydantoin type epoxy resin.

[0025] The mass ratio of the diluent to the matrix epoxy resin is (2-70):100.

[0026] This invention provides a silicone-modified epoxy resin, wherein the raw materials of the silicone-modified epoxy resin include epoxy resin, silicone-modified aliphatic amine curing agent, and silicone-modified epoxy resin diluent;

[0027] The organosilicon-modified aliphatic amine curing agent includes compounds with structures shown in formula (I) and / or formula (II) among organosilicon compounds containing imide bonds as described in any of the above technical solutions.

[0028] The organosilicon-modified epoxy resin diluent includes compounds with structures of formula (II) and / or formula (III) among the organosilicon compounds containing imide bonds described in any of the above technical solutions.

[0029] Preferably, the organosilicon-modified epoxy resin comprises, by weight parts of raw materials:

[0030]

[0031]

[0032] Preferably, the organosilicon-modified aliphatic amine curing agent includes at least a compound of formula (I) from the organosilicon class of compounds;

[0033] The accelerator includes one or more of benzyldimethylamine, 2-ethyl-4-methylimidazolium, 4,4-dimethylaminopyridine, triphenylphosphine, tris(dimethylaminomethyl)phenol, m-phenylenediamine, and p-phenylenediamine;

[0034] The coupling agent includes one or more of KH-540, KH-550, KH-560, KH-570, KH-602, KH-791, KH-792, KH-551, KH-580, A-151, A-171 and A-172;

[0035] The curing temperature of the silicone-modified epoxy resin is 30–200°C.

[0036] The curing time of the silicone-modified epoxy resin is 5 min to 8 h.

[0037] The present invention also provides the application of organosilicon compounds containing imide bonds as described in any one of the above technical solutions or organosilicon-modified epoxy resins as described in any one of the above technical solutions in the field of coating agents.

[0038] This invention provides an organosilicon compound containing imide bonds, wherein the organosilicon compound containing imide bonds has a structure as shown in formula (I), formula (II), or formula (III). Compared with the prior art, this invention addresses the aforementioned shortcomings of existing epoxy resin coating agents for soft magnetic metal composite materials, and obtains an organosilicon-modified epoxy resin coating agent that is inexpensive, environmentally friendly, easy to prepare, and possesses high and low temperature resistance. This invention specifically designs an organosilicon compound containing imide bonds with a specific structure, which can be obtained through steps such as condensation reactions. This compound is used as a fatty amine curing agent containing imide bonds and an organosilicon structure, and as an epoxy resin diluent with adjustable functionality containing imide bonds and an organosilicon structure, thereby obtaining a high-toughness and high-temperature resistant epoxy resin. Using the method of this invention, various epoxy resin curing agents and epoxy resin diluents containing organosilicon bonds and imide bonds can be successfully prepared, with convenient synthesis methods and a wide variety of synthesized epoxy resins. Moreover, the organosilicon-modified epoxy resin prepared by this invention has adjustable viscosity, excellent mechanical properties, and high temperature resistance, making it suitable for working scenarios such as insulation coating of metal soft magnetic composite materials.

[0039] The silicone-modified epoxy resin provided by this invention incorporates silicone segments and imide rings in its structural design, simultaneously increasing the toughness and heat resistance of the epoxy resin, thereby improving the overall performance of the metal soft magnetic composite material. Furthermore, the silicone-modified epoxy resin structure of this invention contains both aromatic imide structures and siloxane structures with different chain lengths. The presence of aromatic imide rings increases the stability of the molecular structure and enhances the orientation of the polymer molecular chains through π-π interactions, thus increasing the polymer's heat resistance. Simultaneously, the introduction of siloxane structures effectively improves the flexibility and toughness of the epoxy resin molecular chains. The introduction of these two structures allows the epoxy resin to meet the requirements of high and low temperature operating conditions. In addition, the silicone-modified epoxy resin curing agent and epoxy resin diluent provided by this invention have rich and diverse structures. Introducing this new structure into the matrix epoxy resin allows for the formulation of various types of epoxy resins to meet the performance requirements of epoxy resins under different operating conditions.

[0040] The organosilicon-modified epoxy resin prepared by this invention has adjustable viscosity, excellent mechanical properties, and high temperature resistance, making it more suitable for applications such as insulating coating of soft magnetic metal composite materials. Furthermore, the preparation method is simple, highly controllable, requires no precious metal catalysts, is environmentally friendly, and inexpensive, making it more suitable for industrial production and application.

[0041] Experimental results show that the silicone-modified epoxy resin prepared by the method of the present invention has a wide range of epoxy value control, ranging from 0.60 to 0.85; the viscosity of the silicone-modified epoxy resin is suitable, ranging from 5000 to 8500 mPa·s; the glass transition temperature of the epoxy resin is significantly increased, reaching 230±5℃; and the shear strength is greatly improved, reaching 10–12 MPa@200℃ and 3.9–4.7 MPa@250℃. Attached Figure Description

[0042] Figure 1 The 1H NMR spectrum of I-8 prepared using 3,3'-HQDPA and 1,3-bis(3-aminopropyl)tetramethyldisiloxane as starting materials in this invention.

[0043] Figure 2 The nuclear magnetic resonance hydrogen spectrum of III-2 prepared by norbornene anhydride and 1,3-bis(3-aminopropyl)tetramethyldisiloxane as starting materials in this invention;

[0044] Figure 3 The DSC curve of the organosilicon-modified epoxy resin prepared in Example 6 of this invention. Detailed Implementation

[0045] To further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims.

[0046] There are no particular restrictions on the source of any raw materials used in this invention; they can be purchased from the market or prepared using conventional methods known to those skilled in the art.

[0047] There are no particular restrictions on the purity of any raw materials used in this invention, but analytical grade is preferred.

[0048] All raw materials of this invention are conventional in the field, and each brand name and abbreviation is clear and distinct in its relevant application. Those skilled in the art can purchase them from the market or prepare them by conventional methods based on the brand name, abbreviation and corresponding application.

[0049] In all the compound structural formulas of this invention, the connection methods and groups are all conventional connection methods and groups in the art. Each connection method and group is clear and well-defined in its relevant field. Those skilled in the art can clearly and uniquely know the relevant structure to be expressed by this invention based on the connection methods and groups in the structural formula.

[0050] This invention provides an organosilicon compound containing an imide bond, wherein the organosilicon compound containing the imide bond has a structure as shown in formula (I), formula (II) or formula (III):

[0051]

[0052] Among them, equation (I) Selected from

[0053] In equations (II) and (III) Each independently selected

[0054] In equations (I), (II), and (III), n is independently the degree of polymerization.

[0055] In this invention, n is preferably 3 to 10, more preferably 4 to 9, and even more preferably 5 to 8.

[0056] In this invention, the compounds with the structures shown in formula (I) and / or formula (II) are preferably aliphatic amine curing agents containing imide bonds and organosilicon structures.

[0057] In this invention, the compounds with the structures shown in formula (II) and / or formula (III) are preferably epoxy resin diluents with adjustable functionality containing imide bonds and organosilicon structures.

[0058] In this invention, the compound with the structure shown in formula (I) is preferably prepared by a condensation reaction of an aromatic dianhydride monomer and a diamine monomer containing a siloxane segment.

[0059] In this invention, the compound with the structure shown in formula (II) is prepared by a condensation reaction and an epoxidation reaction of a dianhydride monomer containing an unsaturated double bond and a diamine monomer containing a siloxane segment.

[0060] In this invention, the compound with the structure shown in formula (III) is prepared by a dianhydride monomer containing an unsaturated double bond and a diamine monomer containing a siloxane segment through a condensation reaction, a substitution reaction and an epoxidation reaction.

[0061] In this invention, the aromatic dianhydride monomer preferably includes one or more of PMDA, BPDA, α-BPDA, DSDA, 6FDA, ODPA, BTDA, and 3,3'-HQDPA, more preferably PMDA (pyromellitic dianhydride), BPDA (3,3',4,4'-biphenyltetracarboxylic dianhydride), α-BPDA (2,3,3',4'-biphenyltetracarboxylic dianhydride), DSDA (3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride), 6FDA (4,4'-(hexafluoroisopropene)phthalic anhydride), ODPA (4,4'-oxybisphthalic anhydride), BTDA (3,3',4,4'-benzophenone tetracarboxylic dianhydride) or 3,3'-HQDPA (2,2',3,3'-triphenyl diether tetracarboxylic dianhydride).

[0062] Correspondingly, in this invention, The groups selected correspond to the aromatic dianhydride monomers from the raw materials:

[0063]

[0064] In this invention, the diamine monomer containing a siloxane segment includes one or more of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, aminopropyl-terminated polydimethylsiloxane, and YASI series polydimethylsiloxane diamine monomers, more preferably 1,3-bis(3-aminopropyl)tetramethyldisiloxane, aminopropyl-terminated polydimethylsiloxane, or YASI series polydimethylsiloxane diamine monomers. Specifically, the YASI series polydimethylsiloxane diamine monomers preferably include one or more of YASI4W, YASI248-99, YAS1248-95, and YASI1000. The YASI series diamine monomers are specifically purchased from Zhejiang Yingruiyun New Material Technology Co., Ltd. The aminopropyl-terminated polydimethylsiloxane is preferably purchased from Hubei Xinmingtai Chemical Co., Ltd.

[0065] Correspondingly, in this invention, The specific choice of functional groups corresponds to the polysiloxane structure in diamine monomers containing siloxane segments.

[0066] In this invention, the dianhydride monomer containing unsaturated double bonds preferably includes one or more of norbornene, 2,3-cyclohexenedian anhydride and 3,4-cyclohexenedian anhydride, more preferably norbornene, 2,3-cyclohexenedian anhydride or 3,4-cyclohexenedian anhydride.

[0067] Correspondingly, in this invention, The chosen functional groups correspond to dianhydride monomers containing unsaturated double bonds in the raw materials:

[0068]

[0069] This invention provides the application of organosilicon compounds containing imide bonds, as described in any one of the above technical solutions, in organosilicon-modified epoxy resins.

[0070] In this invention, the application includes the use of compounds with structures shown in formula (I) and / or formula (II) as curing agents.

[0071] In this invention, the mass ratio of the curing agent to the matrix epoxy resin is preferably (10-120):100, more preferably (10-100):100, and even more preferably (50-80):100.

[0072] In this invention, the application includes the use of compounds with structures shown in formula (II) and / or formula (III) as diluents.

[0073] In this invention, the epoxy resin preferably includes one or more of bisphenol A type, bisphenol F type, bisphenol S type, hydrogenated bisphenol A type, phenolic epoxy resin, aliphatic epoxy resin, glycidylamine type epoxy resin and hydantoin type epoxy resin, more preferably bisphenol A type, bisphenol F type, bisphenol S type, hydrogenated bisphenol A type, phenolic epoxy resin, aliphatic epoxy resin, glycidylamine type epoxy resin or hydantoin type epoxy resin.

[0074] In this invention, the mass ratio of the diluent to the matrix epoxy resin is preferably (2-70):100, more preferably (10-50):100, and even more preferably (20-30):100.

[0075] This invention provides a silicone-modified epoxy resin, wherein the raw materials of the silicone-modified epoxy resin include epoxy resin, silicone-modified aliphatic amine curing agent, and silicone-modified epoxy resin diluent.

[0076] In this invention, the organosilicon-modified aliphatic amine curing agent preferably includes compounds with structures shown in formula (I) and / or formula (II) among organosilicon compounds containing imide bonds as described in any of the above technical solutions.

[0077] In this invention, the organosilicon-modified epoxy resin diluent includes compounds with structures of formula (II) and / or formula (III) among the organosilicon compounds containing imide bonds described in any of the above technical solutions.

[0078] In this invention, the organosilicon-modified epoxy resin comprises, by weight parts of raw materials:

[0079]

[0080] In this invention, the amount of epoxy resin added is preferably 100 parts by weight, more preferably 90 parts by weight, and even more preferably 80 parts by weight.

[0081] In this invention, the amount of the organosilicon-modified fatty amine curing agent added is preferably 10 to 120 parts by weight, more preferably 30 to 100 parts by weight, and even more preferably 50 to 80 parts by weight.

[0082] In this invention, the amount of the silicone-modified epoxy resin diluent added is preferably 2 to 70 parts by weight, more preferably 10 to 50 parts by weight, and even more preferably 20 to 30 parts by weight.

[0083] In this invention, the amount of the accelerator added is preferably 1 to 30 parts by weight, more preferably 5 to 25 parts by weight, and even more preferably 10 to 20 parts by weight.

[0084] In this invention, the amount of coupling agent added is preferably 0 to 20 parts by weight, more preferably 4 to 16 parts by weight, and even more preferably 8 to 12 parts by weight.

[0085] In this invention, the organosilicon-modified aliphatic amine curing agent preferably includes at least a compound of formula (I) from the organosilicon class.

[0086] In this invention, the accelerator preferably includes one or more of benzyldimethylamine, 2-ethyl-4-methylimidazole, 4,4-dimethylaminopyridine, triphenylphosphine, tris(dimethylaminomethyl)phenol, m-phenylenediamine, and p-phenylenediamine, more preferably benzyldimethylamine, 2-ethyl-4-methylimidazole, 4,4-dimethylaminopyridine, triphenylphosphine, tris(dimethylaminomethyl)phenol, m-phenylenediamine, or p-phenylenediamine.

[0087] In this invention, the coupling agent preferably includes one or more of KH-540, KH-550, KH-560, KH-570, KH-602, KH-791, KH-792, KH-551, KH-580, A-151, A-171, and A-172, more preferably KH-540, KH-550, KH-560, KH-570, KH-602, KH-791, KH-792, KH-551, KH-580, A-151, A-171, or A-172.

[0088] In this invention, the curing temperature of the silicone-modified epoxy resin is preferably 30-200℃, more preferably 60-170℃, and even more preferably 90-140℃.

[0089] In this invention, the curing time of the silicone-modified epoxy resin is preferably 5 min to 8 h, more preferably 0.5 to 6 h, more preferably 1 to 5 h, and even more preferably 2 to 4 h.

[0090] The present invention also provides a silicone-modified epoxy resin coating agent, wherein the raw materials of the silicone-modified epoxy resin coating agent include epoxy resin, silicone-modified fatty amine curing agent and silicone-modified epoxy resin diluent.

[0091] In this invention, the organosilicon-modified epoxy resin coating agent preferably corresponds one-to-one with the organosilicon-modified epoxy resin in terms of specific selection and preferred content, which will not be elaborated here.

[0092] This invention aims to complete and refine the overall technical solution, better ensure the structure and composition of organosilicon compounds containing imide bonds, better ensure the composition of organosilicon-modified epoxy resins, and further improve the viscosity adjustability, mechanical properties, and temperature resistance of organosilicon-modified epoxy resins, as well as their coating properties. Preferably, the aforementioned organosilicon-modified epoxy resin and its preparation method include the following:

[0093] The organosilicon-modified epoxy resin provided by this invention comprises:

[0094] (1) Matrix epoxy resin

[0095] (2) Organosilicon-modified aliphatic amine curing agents (Formula I, Formula II)

[0096] (3) Organosilicon-modified epoxy resin diluents (Formula II, Formula III)

[0097] (4) Accelerator

[0098] (5) Coupling agent

[0099]

[0100] Specifically, the matrix epoxy resin includes one or more of the following: bisphenol A type, bisphenol F type, bisphenol S type, hydrogenated bisphenol A type, phenolic epoxy resin, aliphatic epoxy resin, glycidylamine type, and hydantoin type epoxy resin.

[0101] Specifically, the structure of the organosilicon-modified aliphatic amine curing agent is shown in Formula I and Formula II.

[0102] Specifically, the curing agent is prepared by condensation reaction of different types of aromatic dianhydride monomers with diamine monomers containing different siloxane segment lengths.

[0103] Specifically, the aromatic dianhydride monomers used include commercially available dianhydride monomers such as PMDA, BPDA, α-BPDA, DSDA, 6FDA, ODPA, BTDA, and 3,3'-HQDPA.

[0104] Specifically, the siloxane-containing diamine monomers used include 1,3-bis(3-aminopropyl)tetramethyldisiloxane, aminopropyl-terminated polydimethylsiloxane, YASI4W, YASI248-99, YAS1248-95, and YASI1000. By orthogonal experiments with the above dianhydride monomers and diamine monomers, a variety of novel aliphatic amine curing agents with diverse structures can be prepared.

[0105] Specifically, the structure of the organosilicon-modified epoxy resin diluent is shown in Formulas II and III.

[0106] Specifically, the diluent is prepared by a condensation reaction of a dianhydride monomer containing an unsaturated double bond and a diamine monomer containing different siloxane segment lengths. More specifically, the compound with the structure shown in formula (II) is prepared by a condensation reaction and an epoxidation reaction of a dianhydride monomer containing an unsaturated double bond and a diamine monomer containing a siloxane segment. The compound with the structure shown in formula (III) is prepared by a condensation reaction, a substitution reaction, and an epoxidation reaction of a dianhydride monomer containing an unsaturated double bond and a diamine monomer containing a siloxane segment.

[0107] Specifically, the dianhydride monomers used include norbornene anhydride, 2,3-cyclohexene dianhydride, and 3,4-cyclohexene dianhydride. Specifically, the diamine monomers used include 1,3-bis(3-aminopropyl)tetramethyldisiloxane, aminopropyl-terminated polydimethylsiloxane, YASI4W, YASI248-99, YAS1248-95, and YASI1000. By orthogonal experiments with the above dianhydride monomers and diamine monomers, a variety of novel epoxy resin diluents with tunable functionality can be prepared.

[0108] Specifically, the accelerators include benzyl dimethylamine (BDMA), 2-ethyl-4-methylimidazole (EMI), 4,4-dimethylaminopyridine (DMAP), triphenylphosphine (TPP) or tris(dimethylaminomethyl)phenol (TAP), m-phenylenediamine, p-phenylenediamine, etc.

[0109] Specifically, the coupling agents include KH-540, KH-550, KH-560, KH-570, KH-602, KH-791, KH-792, KH-551, KH-580, A-151, A-171 and A-172.

[0110] Specifically, the matrix epoxy resin, organosilicon-modified aliphatic amine curing agent, organosilicon-modified epoxy resin diluent, accelerator, and coupling agent are in the following weight ratio: 100:10-120:2-70:1-30:0-20.

[0111] Specifically, the organosilicon-modified fatty amine curing agent has a weight ratio of 10-120, preferably 20-80.

[0112] Specifically, the organosilicon-modified epoxy resin diluent is present in parts by weight of 2 to 70, preferably 15 to 50.

[0113] Specifically, the accelerator is present in parts by weight of 1 to 30, preferably 3 to 10.

[0114] Specifically, the coupling agent is present in a weight ratio of 0 to 20, preferably 2 to 10.

[0115] Specifically, the curing temperature of the epoxy resin is 30–200°C, preferably 70–150°C.

[0116] Specifically, the curing time of the epoxy resin is 5 min to 8 h, preferably 2 h to 6 h.

[0117] The present invention provides a method for preparing a high-toughness and high-low temperature resistant organosilicon-modified epoxy resin coating agent, which involves preparing an aliphatic amine curing agent containing imide bonds and an organosilicon structure and an epoxy resin diluent containing imide bonds and an organosilicon structure through a condensation reaction, and then combining the two with a matrix epoxy resin, an accelerator, and a coupling agent to obtain an epoxy resin with adjustable viscosity, high-low temperature resistance, and toughening.

[0118] Specifically, the silicone-modified epoxy resin of the present invention comprises: a matrix epoxy resin, a silicone-modified aliphatic amine curing agent (Formula I, Formula II), a silicone-modified epoxy resin diluent (Formula II, Formula III), an accelerator, and a coupling agent.

[0119] Specifically, the structure of the organosilicon-modified fatty amine curing agent of the present invention is shown in Formula I and Formula II.

[0120] Specifically, the structure of the organosilicon-modified epoxy resin diluent of the present invention is shown in Formula II and Formula III.

[0121] Further:

[0122] Synthesis of Organosilicon Modified Epoxy Resin Curing Agent

[0123] Amino acids containing both amide and carboxyl groups are prepared by condensation reaction of pretreated dianhydrides and diamines containing siloxane segments. Then, unreacted free amino groups are protected by functional group protection. Subsequently, an imidizing agent is added to convert the amino acid structure into an imide structure. Finally, the protection is removed to obtain an aliphatic amine curing agent of formula I containing both an imide structure and siloxane segments.

[0124] Synthesis of Organosilicon Modified Epoxy Resin Diluent

[0125] A amide acid containing both amide and carboxyl groups was prepared by condensation reaction of a pretreated dianhydride containing unsaturated double bonds and a diamine containing siloxane segments. The unreacted free amino group was then protected by functional group protection. An imidizing agent was added to convert the amide acid structure into an imide intermediate. The intermediate was oxidized with hydrogen peroxide to obtain an epoxy compound, which was then deprotected to yield an epoxy diluent of formula II.

[0126] The imide intermediate in Formula II undergoes a substitution reaction with epichlorohydrin to yield an epoxy compound of Formula III containing trifunctionality.

[0127] Implementation methods of silicone-modified epoxy resin

[0128] The matrix epoxy resin, organosilicon-modified aliphatic amine curing agent, organosilicon-modified epoxy resin diluent, accelerator, and coupling agent are in the following weight ratio: 100:10~120:2~70:1~30:0~20.

[0129] The matrix epoxy resin, silicone-modified epoxy resin diluent, and coupling agent are mixed evenly and used as component A, while the accelerator and silicone-modified aliphatic amine curing agent are used as component B.

[0130] When using, mix component A and component B evenly according to their weight proportions and then cure them under specific temperature conditions.

[0131] The present invention also provides the application of organosilicon compounds containing imide bonds as described in any one of the above technical solutions or organosilicon-modified epoxy resins as described in any one of the above technical solutions in the field of coating agents.

[0132] In this invention, the coating agent preferably includes a coating agent for preparing soft magnetic metal composite materials, and more preferably a coating agent for insulating coating of soft magnetic metal composite materials.

[0133] In this invention, the coating agent is preferably a silicone-modified epoxy resin coating agent with high toughness and resistance to high and low temperatures.

[0134] The insulating coating process is a crucial step in the preparation of soft magnetic metal composite materials, and it is key to controlling the thickness and uniformity of the insulating coating layer. The physicochemical properties of the insulating coating layer significantly affect the density, mechanical strength, effective permeability, and magnetic loss of the soft magnetic metal composite material.

[0135] This invention provides an organosilicon compound containing imide bonds, its application in organosilicon-modified epoxy resins, and the application of organosilicon compounds or organosilicon-modified epoxy resins in the field of coating agents. The invention specifically designs organosilicon compounds with imide bonds containing specific structures, which can be obtained through steps such as condensation reactions. These compounds are used as aliphatic amine curing agents containing imide bonds and organosilicon structures, and as epoxy resin diluents with adjustable functionality containing imide bonds and organosilicon structures, thereby obtaining a high-toughness and high-temperature resistant epoxy resin. Using the method of this invention, various epoxy resin curing agents and epoxy resin diluents containing organosilicon bonds and imide bonds can be successfully prepared. The synthesis method is convenient and produces a wide variety of epoxy resins. Furthermore, the organosilicon-modified epoxy resin prepared by this invention has adjustable viscosity, excellent mechanical properties, and high temperature resistance, making it suitable for applications such as insulating coating of soft magnetic metal composite materials.

[0136] The silicone-modified epoxy resin provided by this invention incorporates silicone segments and imide rings in its structural design, simultaneously increasing the toughness and heat resistance of the epoxy resin, thereby improving the overall performance of the metal soft magnetic composite material. Furthermore, the silicone-modified epoxy resin structure of this invention contains both aromatic imide structures and siloxane structures with different chain lengths. The presence of aromatic imide rings increases the stability of the molecular structure and enhances the orientation of the polymer molecular chains through π-π interactions, thus increasing the polymer's heat resistance. Simultaneously, the introduction of siloxane structures effectively improves the flexibility and toughness of the epoxy resin molecular chains. The introduction of these two structures allows the epoxy resin to meet the requirements of high and low temperature operating conditions. In addition, the silicone-modified epoxy resin curing agent and epoxy resin diluent provided by this invention have rich and diverse structures. Introducing this new structure into the matrix epoxy resin allows for the formulation of various types of epoxy resins to meet the performance requirements of epoxy resins under different operating conditions.

[0137] The organosilicon-modified epoxy resin prepared by this invention has adjustable viscosity, excellent mechanical properties, and high temperature resistance, making it more suitable for applications such as insulating coating of soft magnetic metal composite materials. Furthermore, the preparation method is simple, highly controllable, requires no precious metal catalysts, is environmentally friendly, and inexpensive, making it more suitable for industrial production and application.

[0138] Experimental results show that the silicone-modified epoxy resin prepared by the method of the present invention has a wide range of epoxy value control, ranging from 0.60 to 0.85; the viscosity of the silicone-modified epoxy resin is suitable, ranging from 5000 to 8500 mPa·s; the glass transition temperature of the epoxy resin is significantly increased, reaching 230±5℃; and the shear strength is greatly improved, reaching 10–12 MPa@200℃ and 3.9–4.7 MPa@250℃.

[0139] To further illustrate the present invention, the following detailed description, in conjunction with embodiments, describes the application of an organosilicon compound containing an imide bond, in organosilicon-modified epoxy resin, and in the field of coating agents. However, it should be understood that these embodiments are implemented under the premise of the technical solution of the present invention, and provide detailed implementation methods and specific operating procedures. They are only for further illustrating the features and advantages of the present invention, and are not intended to limit the scope of the claims of the present invention. The scope of protection of the present invention is not limited to the following embodiments.

[0140] Synthesis Examples of Organosilicon Modified Epoxy Resin Curing Agent I-8

[0141] 1,3-bis(3-aminopropyl)tetramethyldisiloxane (2.0 mol) was weighed into a reaction flask, and dried 3,3'-HQDPA (1.0 mol) was slowly added in tetrahydrofuran as solvent. The reaction was carried out at room temperature for 5 h. Then, Boc₂O (2.4 mol) and Et₃N (3.0 mol) were added to the reaction system, and the reaction was carried out at room temperature for 6 h. Next, Ac₂O (2.5 mol) and Et₃N (3.0 mol) were added to the reaction system, converting the amyl acid structure to an imide structure. Further addition of TFA (3.0 mol) yielded the aliphatic amine curing agent I-8, whose structure is as follows:

[0142]

[0143] The organosilicon-modified epoxy resin curing agent I-8 prepared in this invention was characterized.

[0144] See Figure 1 , Figure 1 The first-order nuclear magnetic resonance (NMR) 1H spectrum of 3,3'-HQDPA and 1,3-bis(3-aminopropyl)tetramethyldisiloxane prepared in this invention is shown.

[0145] Synthesis Examples of Organosilicon Modified Epoxy Resin Diluent II-1

[0146] 1,3-bis(3-aminopropyl)tetramethyldisiloxane (1.0 mol) was weighed into a reaction flask, and dried norbornene adiene anhydride (1.0 mol) was slowly added in tetrahydrofuran solvent. The reaction was carried out at room temperature for 6 h. Then, Boc₂O (1.2 mol) and Et₃N (1.5 mol) were added to the reaction system, and the reaction was carried out at room temperature for 8 h. Next, Ac₂O (1.25 mol) and Et₃N (1.5 mol) were added to the reaction system, converting the amide acid structure to an imide structure. 30% H₂O₂ solution (3.0 mol) was added, and after reacting for 6 h, TFA (1.2 mol) was added to obtain aliphatic amine curing agent II-1, the structure of which is as follows:

[0147]

[0148] Synthesis Examples of Organosilicon Modified Epoxy Resin Diluent III-2

[0149] Weigh 2.0 mol of self-made II-1 into a reaction flask, use DCM as solvent, add 5.0 mol of pyridine, and slowly add 4.0 mol of epichlorohydrin. React at room temperature for 5 h to obtain organosilicon-modified epoxy resin diluent III-2, the structure of which is as follows:

[0150]

[0151] The organosilicon-modified epoxy resin diluent III-2 prepared in this invention was characterized.

[0152] See Figure 2 , Figure 2 The nuclear magnetic resonance (NMR) 1H spectrum of III-2 prepared using norbornene anhydride and 1,3-bis(3-aminopropyl)tetramethyldisiloxane as starting materials in this invention.

[0153] Example 1

[0154] Component A was prepared by uniformly mixing bisphenol A type epoxy resin E55, silicone-modified epoxy resin diluent II-1, and coupling agent KH550 in a weight ratio of 100:18:3. Component B was prepared by uniformly mixing accelerator benzyl dimethylamine and silicone-modified aliphatic amine curing agent I-2 in a weight ratio of 5:28. The epoxy value of the epoxy resin was tested to be 0.68, and the viscosity was 5360 mPa·s. After uniformly mixing components A and B in the specified weight ratio and curing at 90℃ for 6 hours, the cured silicone-modified epoxy resin exhibited a glass transition temperature of 228℃, a shear strength of 10.2 MPa at 200℃, and 3.9 MPa at 250℃.

[0155] The structural formula of curing agent I-2 is:

[0156]

[0157] Example 2

[0158] Component A was prepared by uniformly mixing hydantoin-type epoxy resin MHR070, silicone-modified epoxy resin diluent III-2, and coupling agent KH560 in a weight ratio of 100:25:6. Component B was prepared by uniformly mixing accelerator benzyl dimethylamine and silicone-modified aliphatic amine curing agent I-2 in a weight ratio of 3:40. The epoxy value of the epoxy resin was tested to be 0.76, and the viscosity was 6820 mPa·s. After uniformly mixing components A and B in the specified weight ratio and curing at 120℃ for 4 hours, the cured silicone-modified epoxy resin exhibited a glass transition temperature of 235℃, a shear strength of 11.4 MPa at 200℃, and a shear strength of 4.3 MPa at 250℃.

[0159] Example 3

[0160] Component A was prepared by uniformly mixing hydantoin-type epoxy resin MHR154, silicone-modified epoxy resin diluent III-2, and coupling agent KH560 in a weight ratio of 100:35:3. Component B was prepared by uniformly mixing accelerator benzyl dimethylamine and silicone-modified aliphatic amine curing agent I-5 in a weight ratio of 5:60. The epoxy value of the epoxy resin was tested to be 0.72, and the viscosity was 6940 mPa·s. After uniformly mixing components A and B in the specified weight ratio and curing at 120℃ for 5 hours, the cured silicone-modified epoxy resin exhibited a glass transition temperature of 231℃, a shear strength of 10.8 MPa at 200℃, and a shear strength of 4.6 MPa at 250℃.

[0161] The structural formula of curing agent I-5 is:

[0162]

[0163] Example 4

[0164] Component A was prepared by uniformly mixing bisphenol A type epoxy resin E44, silicone-modified epoxy resin diluent II-1, and coupling agent KH570 in a weight ratio of 100:42:7. Component B was prepared by uniformly mixing accelerator benzyl dimethylamine and silicone-modified aliphatic amine curing agent I-6 in a weight ratio of 6:29. The epoxy value of the epoxy resin was tested to be 0.71, and the viscosity was 5970 mPa·s. After uniformly mixing components A and B in the specified weight ratio and curing at 100℃ for 5 hours, the cured silicone-modified epoxy resin exhibited a glass transition temperature of 229℃ and shear strengths of 11.8 MPa at 200℃ and 4.7 MPa at 250℃.

[0165] The structural formula of curing agent I-6 is:

[0166]

[0167] Example 5

[0168] Component A was obtained by uniformly mixing phenolic epoxy resin F44, silicone-modified epoxy resin diluent III-3, and coupling agent KH550 in a weight ratio of 100:37:4. Component B was obtained by uniformly mixing accelerator 2-ethyl-4-methylimidazole (EMI) and silicone-modified aliphatic amine curing agent I-2 in a weight ratio of 7:45. The epoxy value of the epoxy resin was tested to be 0.78, and the viscosity was 7630 mPa·s. After uniformly mixing components A and B in the specified weight ratio and curing at 100℃ for 5 hours, the cured silicone-modified epoxy resin exhibited a glass transition temperature of 231℃, a shear strength of 11.6 MPa at 200℃, and a shear strength of 4.3 MPa at 250℃.

[0169] The structural formula of epoxy resin diluent III-3 is:

[0170]

[0171] Example 6

[0172] Component A was prepared by uniformly mixing type A epoxy resin E44, silicone-modified epoxy resin diluent III-5, and coupling agent KH550 in a weight ratio of 100:27:6. Component B was prepared by uniformly mixing accelerator benzyl dimethylamine and silicone-modified aliphatic amine curing agent I-2 in a weight ratio of 4:37. The epoxy value of the epoxy resin was tested to be 0.74, and the viscosity was 8210 mPa·s. After uniformly mixing components A and B in the specified weight ratio and curing at 110℃ for 5 hours, the cured silicone-modified epoxy resin exhibited a glass transition temperature of 232℃, a shear strength of 11.3 MPa at 200℃, and a shear strength of 4.6 MPa at 250℃.

[0173] The structural formula of epoxy resin diluent III-5 is:

[0174]

[0175] See Figure 3 , Figure 3 The DSC curve of the organosilicon-modified epoxy resin prepared in Example 6 of this invention.

[0176] Example 7

[0177] Component A was prepared by uniformly mixing type A epoxy resin E44, silicone-modified epoxy resin diluent III-3, and coupling agent KH560 in a weight ratio of 100:32:3. Component B was prepared by uniformly mixing accelerator 2-ethyl-4-methylimidazole (EMI) and silicone-modified aliphatic amine curing agent I-4 in a weight ratio of 5:57. The epoxy value of the epoxy resin was tested to be 0.76, and the viscosity was 7560 mPa·s. After uniformly mixing components A and B in the specified weight ratio and curing at 120℃ for 5 hours, the cured silicone-modified epoxy resin exhibited a glass transition temperature of 231℃, a shear strength of 11.2 MPa at 200℃, and a shear strength of 4.1 MPa at 250℃.

[0178] The structural formula of curing agent I-4 is:

[0179]

[0180] Example 8

[0181] Component A was prepared by uniformly mixing bisphenol A type epoxy resin E51, silicone-modified epoxy resin diluent III-3, and coupling agent KH550 in a weight ratio of 100:42:7. Component B was prepared by uniformly mixing accelerator benzyl dimethylamine and silicone-modified aliphatic amine curing agent I-8 in a weight ratio of 7:73. The epoxy value of the epoxy resin was tested to be 0.79, and the viscosity was 8410 mPa·s. After uniformly mixing components A and B in the specified weight ratio and curing at 120℃ for 4 hours, the cured silicone-modified epoxy resin exhibited a glass transition temperature of 234℃, a shear strength of 11.4 MPa at 200℃, and 4.7 MPa at 250℃.

[0182] Example 9

[0183] Component A was prepared by uniformly mixing hydantoin-type MHR-154B, silicone-modified epoxy resin diluent III-3, and coupling agent KH550 in a weight ratio of 100:36:5. Component B was prepared by uniformly mixing accelerator 2-ethyl-4-methylimidazole (EMI) and silicone-modified fatty amine curing agent I-5 in a weight ratio of 7:64. The epoxy value of the epoxy resin was tested to be 0.81, and the viscosity was 8470 mPa·s. After uniformly mixing components A and B in the specified weight ratio and curing at 120℃ for 5 hours, the cured silicone-modified epoxy resin exhibited a glass transition temperature of 230℃ and shear strengths of 10.7 MPa at 200℃ and 3.9 MPa at 250℃.

[0184] Comparative Example 1

[0185] Bisphenol A type epoxy resin E51, epoxy resin diluent E03, and coupling agent KH550 were mixed evenly in a weight ratio of 100:30:10 to obtain component A. Activators benzyl dimethylamine and m-phenylenediamine were used as curing agents and mixed evenly in a weight ratio of 3:80 to obtain component B. After testing, the epoxy value of the epoxy resin was 0.83, and the viscosity was 6130 mPa·s. After the components A and B were mixed evenly in the specified weight ratio and cured at 120℃ for 5 hours, the glass transition temperature of the cured epoxy resin was 178℃, and the shear strength was 8.1 MPa@200℃ and 2.4 MPa@250℃.

[0186] The performance of the organosilicon-modified epoxy resin and epoxy resin prepared in the embodiments and comparative examples of the present invention was tested.

[0187] See Table 1, which contains the detection experimental data from the embodiments and comparative examples of the present invention.

[0188] Table 1

[0189]

[0190] The foregoing provides a detailed description of an organosilicon-modified epoxy resin and its application as a coating agent. Specific examples have been used to illustrate the principles and implementation methods of the invention. The descriptions of these embodiments are merely for the purpose of helping to understand the method and core ideas of the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that those skilled in the art can make various improvements and modifications to the invention without departing from its principles, and these improvements and modifications also fall within the scope of protection of the claims. The scope of protection of this patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements that are not different from the wording of the claims, or if they include equivalent structural elements that are not substantially different from the wording of the claims, then these other embodiments should also be included within the scope of the claims.

Claims

1. An organosilicon-modified epoxy resin, characterized in that, The raw materials for the silicone-modified epoxy resin include epoxy resin, silicone-modified fatty amine curing agent, and silicone-modified epoxy resin diluent. The organosilicon-modified aliphatic amine curing agent includes one or more organosilicon compounds containing imide bonds with the structures shown in formulas (I-2), (I-4), (I-6), and (I-8); The organosilicon-modified epoxy resin diluent includes one or more organosilicon compounds containing imide bonds with structures shown in formulas (II-1), (III-2), (III-3), and (III-5); （I-2）、 （I-4）、 （I-6）、 （I-8）、 (II-1)、 (III-2)、 (III-3)、 (III-5)。 2. The organosilicon-modified epoxy resin according to claim 1, characterized in that, The compounds with the structures shown in (I-2), (I-4), (I-6), and (I-8) are prepared by condensation reaction of aromatic dianhydride monomers and diamine monomers containing siloxane segments.

3. The organosilicon-modified epoxy resin according to claim 1, characterized in that, The compound with the structure shown in formula (II-1) is prepared by a condensation reaction and an epoxidation reaction between a monoanhydride monomer containing an unsaturated double bond and a diamine monomer containing a siloxane segment.

4. The organosilicon-modified epoxy resin according to claim 1, characterized in that, The compounds with the structures shown in (III-2), (III-3), or (III-5) are prepared by condensation, substitution, and epoxidation reactions of monoanhydride monomers containing unsaturated double bonds and diamine monomers containing siloxane segments.

5. The organosilicon-modified epoxy resin according to claim 1, characterized in that, The mass ratio of the curing agent to the base epoxy resin is (10~120):100; The epoxy resin includes one or more of the following: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenolic type epoxy resin, aliphatic epoxy resin, glycidylamine type epoxy resin, and hydantoin type epoxy resin.

6. The organosilicon-modified epoxy resin according to claim 1, characterized in that, The mass ratio of the diluent to the matrix epoxy resin is (2~70):

100.

7. The organosilicon-modified epoxy resin according to claim 1, characterized in that, The organosilicon-modified epoxy resin, by mass parts of raw materials, comprises: 100 parts by weight of epoxy resin; 10-120 parts by weight of organosilicon-modified fatty amine curing agent; 2-70 parts by weight of silicone-modified epoxy resin diluent; Accelerator 1-30 parts by weight; Coupling agent 0-20 parts by weight.

8. The organosilicon-modified epoxy resin according to claim 7, characterized in that, The accelerator includes one or more of benzyldimethylamine, 2-ethyl-4-methylimidazolium, 4,4-dimethylaminopyridine, triphenylphosphine, tris(dimethylaminomethyl)phenol, m-phenylenediamine, and p-phenylenediamine; The coupling agent includes one or more of KH-540, KH-550, KH-560, KH-570, KH-602, KH-791, KH-792, KH-551, KH-580, A-151, A-171 and A-172.

9. The organosilicon-modified epoxy resin according to claim 1, characterized in that, The curing temperature of the silicone-modified epoxy resin is 30~200℃; The curing time of the silicone-modified epoxy resin is 5 min to 8 h.

10. The application of the organosilicon-modified epoxy resin according to any one of claims 1 to 9 in the field of coating agents.

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