CN113121586A - Modified maleimide compound and preparation method and application thereof - Google Patents

Modified maleimide compound and preparation method and application thereof Download PDF

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Publication number
CN113121586A
CN113121586A CN201911421022.4A CN201911421022A CN113121586A CN 113121586 A CN113121586 A CN 113121586A CN 201911421022 A CN201911421022 A CN 201911421022A CN 113121586 A CN113121586 A CN 113121586A
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compound
modified maleimide
silane
maleimide compound
modified
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孟运东
罗成
许永静
方克洪
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to CN201911421022.4A priority Critical patent/CN113121586A/en
Priority to PCT/CN2020/086536 priority patent/WO2021134992A1/en
Priority to TW109114940A priority patent/TWI756679B/en
Publication of CN113121586A publication Critical patent/CN113121586A/en
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    • C07F7/02—Silicon compounds
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    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
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    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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Abstract

The invention relates to a modified maleimide compound, a preparation method and application thereof, wherein the modified maleimide compound is prepared from a compound (A) or an amino silane-containing organic metal salt and a compound (B) containing at least two maleimide groups. The silane-containing modified maleimide compound is prepared by pre-polymerizing a compound (B) containing at least two maleimide groups with an amino-containing silane compound (A) or an amino-containing organic metal salt, and when the silane-containing modified maleimide compound is used for a resin composition of a composite material, the silane-containing modified maleimide compound has better compatibility with low-polarity resin, avoids volatilization of a silane coupling agent in the drying process of a prepreg, can reduce reactivity between bismaleimide and other resins, reduces curing stress of the resin composition, increases adhesion of the resin composition to a reinforcing material or a conductive layer, and keeps low dielectric loss and high heat resistance.

Description

Modified maleimide compound and preparation method and application thereof
Technical Field
The invention relates to the technical field of printed circuits, in particular to a modified maleimide compound and a preparation method and application thereof.
Background
With the progress of the electronic and electrical industry and the rapid development of terminal electronics, the development direction of electronic circuit substrates is light, thin, high-performance, high-reliability, environment-friendly and the like. The maleimide resin as a thermosetting polyimide resin has excellent mechanical properties, electrical properties, heat resistance and solvent resistance. In electronic circuit substrates, bismaleimide resins or polymaleimide resins have been widely used in the field of packaging substrates. However, one of the problems of the prior art is that the maleimide resin is not sufficient in terms of adhesive force, and therefore, it is generally used in combination with an epoxy resin, a phenol resin and a cyanate resin, which have good adhesive properties, but the adhesive properties of the maleimide resin are still poor when the bismaleimide resin is combined with a resin having low polarity.
CN106700549A discloses a modified bismaleimide resin, a reinforced laminated board and a preparation method thereof, wherein the bismaleimide resin is modified by cyanate ester resin, rubber, dicyandiamide and silicon dioxide to obtain the modified bismaleimide resin, the modified bismaleimide resin is used as an adhesive, glass fiber is used as a base material, and the reinforced laminated board is prepared by dip coating, gluing, adhesive tape drying and laminating. The invention has the advantages that the modified bismaleimide resin which can meet the requirement of industrial production is provided, the reinforced laminated board prepared from the modified bismaleimide resin and the glass fiber has good heat resistance, remarkably improved mechanical property and excellent comprehensive performance, and can be applied to the fields of electrical insulation, aerospace and the like. However, the laminated board obtained in the invention still has the problems of high dielectric constant and high dielectric loss.
CN105295048A discloses a high heat-resistant liquid modified bismaleimide resin and a preparation method thereof, which comprises the steps of carrying out Michael addition melt copolymerization on 3-aminobenzocyclobutene and a bismaleimide monomer to form a prepolymer, cooling, adding an active diluent for heat preservation, cooling, adding a solution in which a catalyst is dissolved, uniformly mixing, and carrying out vacuum evaporation to remove a solvent in which the catalyst is dissolved, thereby obtaining the high heat-resistant liquid modified bismaleimide resin. The resin system provided by the invention is in a flowing liquid state at normal temperature, is an uncommon variety in the field of bismaleimide resin, has good processing manufacturability, is suitable for the forming process of various composite materials at present, not only can be used as the base resin of a high-grade copper-clad plate, but also can be used as an advanced composite material or a high-temperature-resistant adhesive in the fields of aerospace, transportation and the like. However, the composition of bismaleimide resin and low polarity resin of the present invention has poor adhesion to copper foil, glass fiber cloth and other materials, and the resulting laminate has low peel strength.
CN101824148A discloses bismaleimide-triazine resin containing octavinyl polyhedral oligomeric silsesquioxane and a preparation method thereof. Slowly adding 100 parts by weight of bismaleimide into O, O' -diallyl bisphenol A at 120-140 ℃ to obtain a prepolymer I; slowly adding 1894 parts of octavinyl cage-type silsesquioxane into the prepolymer I at 120-140 ℃ to obtain a prepolymer II; 215-280 parts of cyanate ester is weighed and slowly added into the prepolymer II, the temperature is raised to 140-160 ℃, and then the mixture is stirred for 1-2 hours under the condition of heat preservation, so that the bismaleimide-triazine resin containing the octavinyl polyhedral oligomeric silsesquioxane is obtained. The prepared resin can be used as a base material for preparing high-performance copper clad laminates and the like in the field of electronic information. But the resin has poor cohesiveness, and the prepared copper-clad plate has low peel strength.
Therefore, there is a need in the art to develop a novel maleimide compound, which improves the adhesive property in combination with a low-polarity resin and gives a low-dielectric and high-heat-resistant laminate.
Disclosure of Invention
It is an object of the present invention to provide a modified maleimide compound which improves the adhesion properties in combination with a low-polarity resin, and further produces a laminate having high peel strength, low dielectric constant and high heat resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the present invention provides a modified maleimide compound prepared from a compound (a) having a molecular structure as follows or an amino silane-containing organometallic salt, and a compound (B) containing at least two maleimide groups:
Figure BDA0002352393480000031
the R is1、R2And R3Each independently selected from C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) alkyl;
the structure of Y is-Y1-Y2-or
Figure BDA0002352393480000032
Said Y is1And Y2Each independently selected from-CH2-、-C2H4-、-C3H6-、-C4H8-、-C5H10-、-C3H6-N-、-C2H4-N-、
Figure BDA0002352393480000033
Figure BDA0002352393480000034
Figure BDA0002352393480000035
Any one of the above;
said Y is3Is selected from-H, -CH3、-C2H5、-C3H7、-C4H9、-C5H11、-C8H17、-C15H31、
Figure BDA0002352393480000036
Figure BDA0002352393480000037
Any one of the above;
and m is 0 or 1.
The invention carries out heating reaction on a compound (B) containing at least two maleimide groups and an amino-containing silane compound (A) or an amino-containing organic metal salt to obtain a silane-containing modified maleimide compound. When the modified bismaleimide silane coupling agent is used for a resin composition of a composite material, the modified bismaleimide silane coupling agent has better compatibility with a low-polarity resin, avoids volatilization of the silane coupling agent in the drying process of a prepreg, can reduce reactivity between bismaleimide and other resins, reduces curing stress of the resin composition, increases adhesion of the resin composition to a reinforcing material or a conductive layer, and maintains low dielectric loss and high heat resistance.
In the present invention, the N atom of the compound (A) or the organometallic salt of aminosilane is ortho-linked to the carbonyl group in the compound (B), and a modified maleimide compound of the following structure can be formed as an example:
Figure BDA0002352393480000041
the above structure is merely for describing the connection mode after the reaction of the compound (a) or the organic metal salt of aminosilane and the compound (B), and is not limited to the above structure, and the structure of the obtained modified maleimide compound may be different depending on the structure of the raw material.
Preferably, the compound (a) has any one of the structures shown in formulae I to III below:
Figure BDA0002352393480000042
Figure BDA0002352393480000051
the R is1、R2、R3、Y1、Y2And Y3All having the same selection ranges as before.
Preferably, said R is1、R2And R3Each independently selected from CH3、C2H5Or C3H7Any one of them.
Preferably, said Y is1And Y2Each independently selected from
Figure BDA0002352393480000052
Figure BDA0002352393480000053
Figure BDA0002352393480000054
Any one of them.
The compound (A) preferably contains the connecting groups, the connecting groups can prolong the chain length, the influence of a cross-linked structure of the resin after curing on siloxane is avoided, the bonding performance of the resin can be further improved, and the main chains of the structures have higher rigidity and are favorable for high heat resistance.
Preferably, the compound (B) has a structure represented by formula IV or formula V below:
Figure BDA0002352393480000055
x is selected from-CH2-、-C2H4-、-C3H6-、-C4H8-、-C5H10-、
Figure BDA0002352393480000056
Figure BDA0002352393480000061
Figure BDA0002352393480000062
Any one of the above;
the R, R4～R11Each independently selected from the group consisting of-H, C1-C15 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14) alkyl, and,
Figure BDA0002352393480000063
Figure BDA0002352393480000064
Any one of them, preferably-H, -CH3、-C2H5、-C3H7、-C4H9、-C5H11、-C8H17、-C15H31、
Figure BDA0002352393480000065
Any one of the above;
n is an integer of 1 to 10, such as 2, 3, 4, 5, 6, 7, 8, 9, and the like.
Another object of the present invention is to provide a method for producing the modified maleimide compound according to the first object, comprising: and carrying out heating reaction on the compound (A) or the amino-containing silane organic metal salt and the compound (B) containing at least two maleimide groups to obtain the modified maleimide compound.
Preferably, the temperature of the heating reaction is 100 to 200 ℃, preferably 110 ℃, 120 ℃, 130 ℃, 136 ℃, 141 ℃, 145 ℃, 151 ℃, 156 ℃, 160 ℃, 165 ℃ and 170 ℃.
Preferably, the heating reaction time is 1-30 h, preferably 2h, 3h, 4h, 5h, 6h, 7h, 8h, 10h, 12h, 16h, 21h and 28 h.
Preferably, the heating reaction is carried out under condensing reflux conditions.
Preferably, the heating reaction is carried out under stirring.
Preferably, the molar ratio of the compound (a) or the aminosilane-containing organometallic salt to the compound (B) is 10:90 to 80:20, for example 10:90, 15:85, 20:80, 24:76, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, etc. In order to allow the compound (a) and the compound (B) to react sufficiently, the molar ratio is more preferably 30:70 to 50:50, for example, 30:70, 35:65, 38:62, 40:60, 45:55, 50:50, and the like.
Preferably, a promoter is added to the heating reaction.
Preferably, the accelerator is used in an amount of 0.01 to 10% by mass of the compound (B), for example, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, etc.
Preferably, the accelerator includes any one or a combination of at least two of dicumyl peroxide, t-butyl cumyl peroxide, di-t-butyl peroxide, t-butyl peroxyisopropyl carbonate, 2, 5-dimethyl-2, 5-di-t-butyl cumyl peroxy hexyne-3, 2, 5-dimethyl 2, 5-di-t-butyl hexane peroxide, p-menthane peroxide, 1-bis (t-amyl peroxy) cyclohexane, diisopropylbenzene hydroperoxide, benzoyl peroxide derivatives, metal salts of acetylacetone, metal salts of naphthenic acid, vanadium pentoxide, amine compounds, quaternary ammonium salts, imidazole, triphenylphosphine, or triphenylphosphine derivatives.
Preferably, a solvent is added to the heating reaction.
Preferably, the amount of the solvent is 10 to 500% by mass of the compound (B), for example, 50%, 100%, 150%, 200%, 250%, 300%, 350%, 400%, 450%, 480%, etc., preferably 50 to 400%;
preferably, the solvent comprises any one or a combination of at least two of toluene, xylene, cyclohexane, tetrahydrofuran, N-Dimethylformamide (DMF), or butanone.
It is a further object of the present invention to provide a resin composition containing the modified maleimide compound according to one of the objects.
The fourth object of the present invention is to provide a prepreg sheet comprising a reinforcing material and the resin composition of the third object attached thereto by impregnation drying.
Preferably, the reinforcing material comprises glass fibre cloth.
The fifth object of the present invention is to provide an insulating plate comprising at least one prepreg sheet of the fourth object.
Still another object of the present invention is to provide a metal-clad laminate including at least one of the prepreg sheets of the fourth object and a metal foil clad on one side or both sides of the laminated prepreg sheets.
A seventh object of the present invention is to provide a printed circuit board comprising at least one prepreg sheet of the fourth object, or at least one insulating sheet of the fifth object, or at least one metal-clad laminate sheet of the sixth object.
Compared with the prior art, the invention has the following beneficial effects:
the invention carries out heating reaction on a compound (B) containing at least two maleimide groups and an amino-containing silane compound (A) or an amino-containing organic metal salt to obtain a silane-containing modified maleimide compound. When the modified bismaleimide silane coupling agent is used for a resin composition of a composite material, the modified bismaleimide silane coupling agent has better compatibility with a low-polarity resin, avoids volatilization of the silane coupling agent in the drying process of a prepreg, can reduce reactivity between bismaleimide and other resins, reduces curing stress of the resin composition, increases adhesion of the resin composition to a reinforcing material or a conductive layer, and maintains low dielectric loss and high heat resistance.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The detailed information of the compounds referred to below is as follows:
KBM-602: n-2- (β -aminoethyl) -3- γ -aminopropylmethyldimethoxysilane, japan believes to be the most probable base;
KBM-603: n-2- (aminoethyl) -3-aminopropyltrimethoxysilane, Japan Beacon;
KBM-903: 3-aminopropyltrimethoxysilane, japan;
KBE-903: 3-aminopropyltriethoxysilane, japan believes;
1, 2-ethylenediamine, N' -dibenzyl-N- [3- (trimethoxysilane) propyl ] -hydrochloride, CAS: 145151-33-3, reagents, commercially available;
KBM-403: 3-glycidyloxypropylmethyltrimethoxysilane, Japan Beacon;
DDM: diaminodiphenylmethane, indian aca;
DDS: diamino diphenyl sulfone, indian acai;
CAS: 92-87-5, 4,4' -diaminobiphenyl, reagent, commercially available;
BMI-50P: multifunctional maleimide resins, japan KI;
BMI-70: bis (3-ethyl-5-methyl-4-maleimidobenzene) methane, japan KI;
BMI-80: 2, 2-bis (4- (4-maleimidophenoxy) phenyl) propane, japan KI.
Synthesis examples 1 to 6
Synthesis examples 1 to 6 provide modified maleimide compounds, which are prepared by the following steps:
adding silane compounds containing amino groups (KBM-602, KBM-603, KBM-903, KBE-903), compounds containing at least two maleimide groups (BMI-70, BMI-80, BMI-50P), an accelerator and a solvent into a reaction vessel with the functions of condensing reflux, stirring and heating, stirring and refluxing, evaporating the solvent in reactants, and cooling to normal temperature to obtain modified maleimide compounds P1-P6.
The raw material composition, reaction time and reaction temperature of synthesis examples 1 to 6 are detailed in Table 1.
TABLE 1
Figure BDA0002352393480000091
Figure BDA0002352393480000101
In Table 1, -.
Synthesis examples 7 to 10
The synthesis example provides modified maleimide compounds P7-P10, and the preparation method comprises the following steps:
adding KBM-403, a diamine compound (DDM, DDS or 4,4' -diaminobiphenyl) and DMF (dimethyl formamide) into a reaction vessel with condensing reflux, stirring and heating, heating to 160 ℃, stirring and refluxing for 2h, then adding a compound (BMI-70 or BMI-50P) containing more than two maleimide groups, heating, stirring and refluxing, evaporating a solvent in a reactant, and cooling to normal temperature to obtain the modified maleimide compound P7-10.
The raw material composition, reaction time and reaction temperature of synthesis examples 7 to 10 are detailed in Table 2.
TABLE 2
Synthesis example 7 Synthesis example 8 Synthesis example 9 Synthesis example 10
P7 P8 P9 P10
KBM-403 6 50 45 50
DDM —— —— —— 30
DDS —— —— 35 ——
4,4' -diaminobiphenyl 4 30 —— ——
BMI-70 90 20 20
BMI-50P —— 20 —— ——
DMF 100 10 20
MEK —— 20 —— ——
Triphenylphosphine —— —— 0.2 0.2
Reaction temperature 100℃ 150℃ 200℃ 160℃
Reaction time 30h 5h 1h 10h
In Table 2, -.
Comparative Synthesis example 1
The modified bismaleimide resin (D1) prepared according to example 1 of patent application CN101775139A was prepared as follows:
mixing 100 parts of bismaleimide, 50 parts of diallyl phenyl compound, 12 parts of gamma-aminopropyl triethoxysilane and 0.50-1.50 parts of water at room temperature, and reacting for 60 minutes at 40 ℃; and then the temperature is increased to 150 ℃, and after prepolymerization reaction is carried out for 120 minutes, modified bismaleimide resin D1 is obtained.
Examples 1 to 10 and comparative examples 1 to 2
Examples 1-10 and comparative examples 1-2 respectively provide a resin glue solution and a laminated board, and the specific preparation process is as follows:
(1) preparation of resin glue solution:
dissolving modified maleimide compound (one of P1-P10 and D1) or unmodified maleimide compound in DMF, and uniformly mixing with other components in the formula to obtain resin glue solution; the specific formulation is detailed in table 3;
(2) preparation of the laminate:
uniformly soaking 2116 glass fiber cloth in the resin glue solution, baking in a forced air oven at 155 deg.C for 5min to obtain prepreg sheets, overlapping 6 sheets of the prepreg sheets, covering with 35 μm reversed copper foil, and pressing in a vacuum hot press at 3MPa and 220 deg.C for 90min to obtain the laminated board.
And (3) performance testing:
(1) glass transition temperature Tg: dynamic thermo-mechanical analysis (DMA) testing was used, with reference to the DMA test method specified by IPC-TM-6502.4.24.
(2) Thermal decomposition temperature (Td): the thermogravimetric analysis (TGA) test was used, with reference to the standard IPC-TM-6502.4.24.6.
(3) Peel Strength (PS): the tensile force required for peeling each millimeter of copper foil from the copper clad laminate at room temperature.
(4) Dielectric constant (Dk) and dielectric loss tangent (Df): measured using a plate capacitance method, referred to the standard IPC-TM-6502.4.24
(5) Flame retardance: according to UL94 "50W (20mm) vertical burning test: v-0, V-1 and V-2' test methods, and V-0 is determined to be flame retardant.
(6) The thermal expansion coefficient and the thermal expansion ratio of 50-260 ℃ are as follows: the test was carried out using a static thermal analyzer (TMA) test, the test being referred to the IPC-TM-6502.4.24 standard.
(7) Thermal stress: the copper bearing laminate was floated on the surface of molten tin at 288 ℃ for delamination or bubbling time as a test result.
The results of the above tests are detailed in Table 3.
TABLE 3
Figure BDA0002352393480000121
Figure BDA0002352393480000131
Figure BDA0002352393480000141
The details of the components in table 3 are as follows:
OPE-2 St: mitsubishi gas, a both-end olefin functionalized polyphenylene ether;
b-1000: japanese soda, polybutadiene resin;
ricon 257: krewiller, usa, butadiene-styrene-divinylbenzene branched terpolymers;
a1536: american kraton, SEBS resin;
NQ 1025J: inorganic filler NQ1025J spherical fused silica, D50 ═ 3.0 μm, new materials inc, biseri, jiang;
Bt-93W: yabao, decabromodiphenylethylene, a flame retardant;
OP 935: clariant, usa, a phosphorus-containing flame retardant;
DCP: dicumyl peroxide and initiator.
Representing no addition of the corresponding substance.
As can be seen from Table 3, the modified maleimide compound provided by the invention has strong bonding property after being combined with low-polarity resin, and the prepared laminated board has high peel strength and good dielectric property and heat resistance, wherein the peel strength is more than 0.8N/mm, the 1GHz dielectric constant is less than 3.8, the 1GHz dielectric loss factor is less than 0.002, the glass transition temperature is more than 190 ℃, the thermal decomposition temperature is more than 400 ℃, the thermal expansion ratio of 50-260 ℃ is less than 2%, and the thermal stress is more than 60 min.
Comparative example 1 the silane compound containing amino group and maleimide were not prepolymerized but added to the resin dope, respectively, and the laminate finally obtained had higher peel strength, lower Tg and Td, higher Dk and Df, higher thermal expansion coefficient and expansion ratio, and significantly reduced heat resistance. This is because, in the course of curing the glue solution, the silane compound containing an amino group volatilizes rapidly, and the curing reaction of bismaleimide with an olefin resin is fast, thereby deteriorating the above-mentioned properties.
The modified maleimide compound used in comparative example 2, which also included a diallylphenyl compound as a starting material, exhibited significantly lower dielectric properties and significantly higher dielectric constant and dielectric loss than those of the examples, because the diallylphenyl compound reacted with bismaleimide more complicated and adversely affected the dielectric properties.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A modified maleimide compound, characterized in that it is prepared from a compound (A) having the following molecular structure or an amino silane-containing organometallic salt, and a compound (B) having at least two maleimide groups:
Figure FDA0002352393470000011
the R is1、R2And R3Each independently selected from C1-C6 alkyl;
the structure of Y is-Y1-Y2-or
Figure FDA0002352393470000012
Said Y is1And Y2Each independently selected from-CH2-、-C2H4-、-C3H6-、-C4H8-、-C5H10-、-C3H6-N-、-C2H4-N-、
Figure FDA0002352393470000013
Figure FDA0002352393470000014
Figure FDA0002352393470000015
Any one of the above;
said Y is3Is selected from-H, -CH3、-C2H5、-C3H7、-C4H9、-C5H11、-C8H17、-C15H31、
Figure FDA0002352393470000016
Figure FDA0002352393470000017
Any one of the above;
and m is 0 or 1.
2. The modified maleimide compound according to claim 1, characterized in that the compound (a) has any one of the structures represented by the following formulae I to III:
Figure FDA0002352393470000021
the R is1、R2、R3、Y1、Y2And Y3All having the same limitations as defined in claim 1.
3. The modified maleimide compound according to claim 1 or 2, wherein R is1、R2And R3Each independently selected from CH3、C2H5Or C3H7Any one of the above;
preferably, said Y is1And Y2Each independently selected from
Figure FDA0002352393470000022
Figure FDA0002352393470000023
Figure FDA0002352393470000024
Any one of them.
4. The modified maleimide compound according to any one of claims 1 to 3, wherein the compound (B) has a structure represented by the following formula IV or formula V:
Figure FDA0002352393470000025
x is selected from-CH2-、-C2H4-、-C3H6-、-C4H8-、-C5H10-、
Figure FDA0002352393470000031
Figure FDA0002352393470000032
Figure FDA0002352393470000033
Any one of the above;
the R, R4～R11Each independently selected from-H, C1-C15 alkyl,
Figure FDA0002352393470000034
Figure FDA0002352393470000035
Any one of them, preferably-H, -CH3、-C2H5、-C3H7、-C4H9、-C5H11、-C8H17、-C15H31、
Figure FDA0002352393470000036
Any one of the above;
and n is an integer of 1-10.
5. A production method of the modified maleimide compound according to any one of claims 1 to 4, characterized by comprising: carrying out heating reaction on the compound (A) or the amino-containing silane organic metal salt and a compound (B) containing at least two maleimide groups to obtain the modified maleimide compound;
preferably, the temperature of the heating reaction is 100-200 ℃;
preferably, the heating reaction time is 1-30 h;
preferably, the heating reaction is carried out under the condition of condensing reflux;
preferably, the heating reaction is carried out under stirring;
preferably, the molar ratio of the compound (A) or the amino silane-containing organic metal salt to the compound (B) is 10: 90-80: 20;
preferably, a promoter is added in the heating reaction;
preferably, the amount of the accelerator is 0.01-10% of the mass of the compound (B);
preferably, the accelerator comprises any one or at least two of dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxyisopropyl carbonate, 2, 5-dimethyl-2, 5-di-tert-butyl cumyl peroxy hexyne-3, 2, 5-dimethyl 2, 5-di-tert-butyl hexane peroxide, p-menthane peroxide, 1-bis (tert-amyl peroxy) cyclohexane, diisopropylbenzene hydroperoxide, benzoyl peroxide derivatives, metal salts of acetylacetone, metal salts of naphthenic acid, vanadium pentoxide, amine compounds, quaternary ammonium salts, imidazole, triphenylphosphine or triphenylphosphine derivatives;
preferably, a solvent is added in the heating reaction;
preferably, the amount of the solvent is 10-500%, preferably 50-400%, of the mass of the compound (B);
preferably, the solvent comprises any one or a combination of at least two of toluene, xylene, cyclohexane, tetrahydrofuran, N-dimethylformamide, or butanone.
6. A resin composition comprising the modified maleimide compound according to any one of claims 1 to 4.
7. A prepreg comprising a reinforcing material and the resin composition according to claim 6 attached thereto by impregnation drying;
preferably, the reinforcing material comprises glass fibre cloth.
8. An insulating panel comprising at least one prepreg according to claim 7.
9. A metal-clad laminate comprising at least one prepreg according to claim 7 and a metal foil clad on one or both sides of the laminated prepreg.
10. A printed circuit board comprising at least one prepreg according to claim 7, or at least one insulating sheet according to claim 8, or at least one metal-clad laminate according to claim 9.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113512057A (en) * 2021-07-20 2021-10-19 山东阳谷华泰化工股份有限公司 Bismaleimide propyl diethoxysilane, and preparation method and application thereof
CN114561101A (en) * 2022-04-01 2022-05-31 焦作市天益科技有限公司 Diallyl bisphenol A modified bismaleimide resin capable of prolonging shelf life and preparation method thereof
CN116120560A (en) * 2022-10-11 2023-05-16 苏州生益科技有限公司 Preparation method of modified bismaleimide prepolymer, resin composition and application of resin composition
WO2024077887A1 (en) * 2022-10-11 2024-04-18 苏州生益科技有限公司 Modified bismaleimide prepolymer, resin composition, and use of resin composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3966531A (en) * 1974-02-05 1976-06-29 Rhone-Poulenc Industries Compositions containing silanes possessing imide groups
JP2002128957A (en) * 2000-10-24 2002-05-09 Yokohama Rubber Co Ltd:The Antioxidant and rubber composition containing the same
CN102584886A (en) * 2012-01-17 2012-07-18 华南理工大学 Silane coupling agent and preparation method thereof
CN103313995A (en) * 2010-12-17 2013-09-18 Sika技术股份公司 Secondary aminosilanes
CN109879903A (en) * 2019-01-09 2019-06-14 青岛科技大学 One kind is novel to prevent old silane coupling agent and preparation method thereof
CN110218415A (en) * 2019-05-31 2019-09-10 广东生益科技股份有限公司 Resin combination, prepreg, laminate, metal-clad laminate and printed wiring board
CN113088061A (en) * 2019-12-23 2021-07-09 广东生益科技股份有限公司 Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102775605A (en) * 2012-08-14 2012-11-14 西北工业大学 Modified bismaleimide resin and preparation method thereof
CN104845363B (en) * 2014-02-14 2017-04-05 广东生益科技股份有限公司 A kind of halogen-free resin composition and application thereof
CN106916418B (en) * 2015-12-25 2020-07-07 广东生益科技股份有限公司 Thermosetting resin composition, prepreg, metal foil-clad laminate and printed circuit board
CN110317541B (en) * 2019-06-19 2021-07-13 南亚新材料科技股份有限公司 Bonding sheet and preparation method of high-speed copper-clad plate

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3966531A (en) * 1974-02-05 1976-06-29 Rhone-Poulenc Industries Compositions containing silanes possessing imide groups
JP2002128957A (en) * 2000-10-24 2002-05-09 Yokohama Rubber Co Ltd:The Antioxidant and rubber composition containing the same
CN103313995A (en) * 2010-12-17 2013-09-18 Sika技术股份公司 Secondary aminosilanes
CN102584886A (en) * 2012-01-17 2012-07-18 华南理工大学 Silane coupling agent and preparation method thereof
CN109879903A (en) * 2019-01-09 2019-06-14 青岛科技大学 One kind is novel to prevent old silane coupling agent and preparation method thereof
CN110218415A (en) * 2019-05-31 2019-09-10 广东生益科技股份有限公司 Resin combination, prepreg, laminate, metal-clad laminate and printed wiring board
CN113088061A (en) * 2019-12-23 2021-07-09 广东生益科技股份有限公司 Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113512057A (en) * 2021-07-20 2021-10-19 山东阳谷华泰化工股份有限公司 Bismaleimide propyl diethoxysilane, and preparation method and application thereof
CN114561101A (en) * 2022-04-01 2022-05-31 焦作市天益科技有限公司 Diallyl bisphenol A modified bismaleimide resin capable of prolonging shelf life and preparation method thereof
CN116120560A (en) * 2022-10-11 2023-05-16 苏州生益科技有限公司 Preparation method of modified bismaleimide prepolymer, resin composition and application of resin composition
CN116120560B (en) * 2022-10-11 2024-04-12 苏州生益科技有限公司 Preparation method of modified bismaleimide prepolymer, resin composition and application of resin composition
WO2024077887A1 (en) * 2022-10-11 2024-04-18 苏州生益科技有限公司 Modified bismaleimide prepolymer, resin composition, and use of resin composition

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