CN112079763B - Modified maleimide compound, and prepreg and laminated board manufactured by using same - Google Patents

Modified maleimide compound, and prepreg and laminated board manufactured by using same Download PDF

Info

Publication number
CN112079763B
CN112079763B CN202010999594.7A CN202010999594A CN112079763B CN 112079763 B CN112079763 B CN 112079763B CN 202010999594 A CN202010999594 A CN 202010999594A CN 112079763 B CN112079763 B CN 112079763B
Authority
CN
China
Prior art keywords
structural formula
prepreg
reactant
compound
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010999594.7A
Other languages
Chinese (zh)
Other versions
CN112079763A (en
Inventor
谌香秀
崔春梅
黄荣辉
戴善凯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Shengyi Technology Co Ltd
Original Assignee
Suzhou Shengyi Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou Shengyi Technology Co Ltd filed Critical Suzhou Shengyi Technology Co Ltd
Priority to CN202010999594.7A priority Critical patent/CN112079763B/en
Publication of CN112079763A publication Critical patent/CN112079763A/en
Application granted granted Critical
Publication of CN112079763B publication Critical patent/CN112079763B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/34—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention develops a novel modified maleimide compound, and experiments prove that: compared with the existing bismaleimide, the prepreg and the laminated board prepared from the bismaleimide have the characteristics of excellent dielectric property, heat resistance, high peel strength, low water absorption rate and thermal expansion coefficient, excellent processing property and the like, can be applied to the fields of IC packaging and high speed and high frequency, have wide application prospects, and lay a foundation for better serving the fields of IC packaging and high speed and high frequency.

Description

Modified maleimide compound, and prepreg and laminated board manufactured by using same
Technical Field
The invention relates to a modified maleimide compound, and a prepreg and a laminated board prepared from the modified maleimide compound, and belongs to the technical field of electronic materials.
Background
With the upgrading of technology, the consumer electronics markets such as automobile markets and smart phones have new requirements on PCBs, and after the 5G commercial market appears in 2018, the requirements of the markets on the dielectric property of PCB base materials are one more step higher, and the high-frequency high-speed copper-clad plate is one of indispensable electronic base materials in the 5G era. In short, the PCB substrate material needs to have a low dielectric constant and dielectric loss tangent to reduce the delay, distortion and loss of signals during high-speed transmission and the interference between signals.
In the prior art, the main components of the resin composition (or single resin) used for the PCB substrate material are epoxy resin and bismaleimide resin. The excellent physical mechanical and electrical insulation performance, the bonding performance with various materials and the flexibility of the use process of the epoxy resin are not possessed by other thermosetting plastics; however, it is difficult to satisfy the application in high frequency because of the high dielectric constant and dielectric loss of the epoxy resin. Bismaleimide resins have excellent heat resistance, peel resistance and high modulus, and are therefore widely used in high performance printed circuit boards; however, the bismaleimide resin commonly used at present is a diamine-modified or allyl-modified bismaleimide resin, and has disadvantages of high curing temperature, high water absorption rate, high dielectric constant/loss value, and the like.
Therefore, it is apparent that development of a novel modified maleimide compound, which can effectively control processability, further reduce water absorption, lower curing temperature, and improve peel strength and thermal expansion coefficient, in addition to having both excellent dielectric properties and heat resistance, has positive practical significance.
Disclosure of Invention
The invention aims to provide a modified maleimide compound.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a modified maleimide compound, the chemical structural formula of which is the following structural formula (1) or structural formula (2):
Figure GDA0003605250550000011
wherein: n is a positive integer of 1-5;
a is a group represented by the following structural formula (3):
Figure GDA0003605250550000021
wherein R is1Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R2Represents an alkylene group having 1 to 10 carbon atoms;
b is a group represented by the following structural formula (4):
Figure GDA0003605250550000022
wherein R is3、R4、R5And R6Any two of which represent a hydrogen atom, the other represents a connecting bond, and the remaining one is a group represented by the following structural formula (5):
Figure GDA0003605250550000023
x is-CH2-，-C(CH3)2-，-C(CF3)2-，-SO2-, -O-or the following structural formula (6):
Figure GDA0003605250550000024
as above, A has a vinylbenzyl group at the terminal.
Further preferably, R is represented by the formula (3)1Represents a hydrogen atom, a methyl group or an ethyl group; the R is2Represents a methylene group, an ethylene group or a propylene group.
Further preferably, the modified maleimide compound is at least one of the following structures (9) to (15):
Figure GDA0003605250550000025
Figure GDA0003605250550000031
the invention also discloses a preparation method of the modified maleimide compound, which comprises the following steps:
s1: reacting acetic acid or acetic anhydride with a compound with amino to obtain a reactant A;
s2: reacting the reactant A with a compound shown as the following structural formula (a) to obtain a reactant B;
Figure GDA0003605250550000041
wherein R is1Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R2Represents an alkylene group having 1 to 10 carbon atoms; further preferably, is
Figure GDA0003605250550000042
S3: reacting the reactant B with ethanol, removing acetic acid and reducing into a reactant C with amino;
s4: and (3) carrying out dehydration ring-closure reaction on the reactant C and maleic anhydride to obtain the modified maleimide.
Preferably, the compound represented by the structural formula (a) is selected from p-chloromethyl styrene, p-chloroethyl styrene, p-bromomethylstyrene, p-bromoethylstyrene, m-chloromethyl styrene, m-chloroethyl styrene, m-bromoethylstyrene or m-bromomethylstyrene.
Preferably, the compound having an amino group is selected from the following structural formula (7) or structural formula (8):
Figure GDA0003605250550000043
y in the structural formula (8) is-CH2-、-C(CH3)2-、-C(CF3)2-、-SO2-, -O-or
Figure GDA0003605250550000044
The invention also claims a resin composition, which comprises a modified maleimide compound and an additive; the chemical structural formula of the modified maleimide compound comprises at least one of the following structural formula (1) and structural formula (2):
Figure GDA0003605250550000045
wherein: n is a positive integer of 1-5;
a is a group represented by the following structural formula (3):
Figure GDA0003605250550000051
wherein R is1Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R2Represents an alkylene group having 1 to 10 carbon atoms;
b is a group represented by the following structural formula (4):
Figure GDA0003605250550000052
wherein R is3、R4、R5And R6Any two of which represent a hydrogen atom, the other represents a connecting bond, and the remaining one is a group represented by the following structural formula (5):
Figure GDA0003605250550000053
x is-CH2-，-C(CH3)2-，-C(CF3)2-，-SO2-, -O-or the following structural formula (6):
Figure GDA0003605250550000054
hereinbefore, the main component of the resin composition is the modified maleimide compound; however, the resin composition may further contain other resins commonly used in the art, such as epoxy resins, benzoxazine resins, cyanate ester resins, maleimide resins (other maleimide resins than the above-mentioned modified maleimide resins), polyphenylene ether resins, phenol resins, polybutadiene, polypentadiene, polystyrene, butadiene-styrene copolymers, styrene-butadiene-styrene copolymers, and the like.
In the above technical scheme, the additive is at least one selected from a filler, a flame retardant, a coupling agent, an accelerator, an initiator, a solvent, a pigment and an auxiliary agent.
The filler is an inorganic filler or an organic filler, and the inorganic filler is at least one selected from fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talcum powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica and glass fiber powder. The organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
The flame retardant may be a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organosilicon flame retardant, an organic metal salt flame retardant, an inorganic flame retardant, or the like. Wherein the bromine flame retardant can be decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalimide. The phosphorus-containing flame retardant may be an inorganic phosphorus, a phosphate ester compound, a phosphoric acid compound, a hypophosphorous acid compound, a phosphorus oxide compound, or an organic phosphorus-containing compound such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ), 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2, 6-dimethylphenyl) phosphorus, phosphazene, or modified phosphazene. The nitrogen-based flame retardant may be a triazine compound, a cyanuric acid compound, an isocyanic acid compound, phenothiazine, or the like. The organic silicon flame retardant can be organic silicon oil, organic silicon rubber, organic silicon resin and the like. The organometallic flame retardant may be ferrocene, acetylacetone metal complexes, organometallic carbonyl compounds, and the like. The inorganic flame retardant may be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, or the like.
The accelerator is at least one selected from 4-dimethylamino pyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole and zinc isooctanoate.
The initiator is selected from one or more of diacyl peroxide, peroxy ketal, peroxycarbonate, peroxyester, ketone peroxide, dialkyl peroxide and hydroperoxide.
The invention also discloses a prepreg prepared by the resin composition, which is prepared by dissolving the resin composition with a solvent to prepare a glue solution, then soaking a reinforcing material in the glue solution, and heating and drying the soaked reinforcing material.
The organic solvent used in the present invention is not particularly limited. For example, the organic solvent may be selected from one or a combination of any of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.
The reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric; preferably, the reinforcing material is glass fiber cloth, and open fiber cloth or flat cloth is preferably used in the glass fiber cloth. In addition, when the reinforcing material is a glass cloth, the glass cloth generally needs to be chemically treated to improve the interface between the resin composition and the glass cloth. The main method of the chemical treatment is a coupling agent treatment. The coupling agent used is preferably an epoxy silane, an aminosilane or the like to provide good water resistance and heat resistance.
The preparation method of the prepreg comprises the following steps: and (2) soaking the reinforcing material in the resin composition glue solution, then baking the soaked reinforcing material for 1-15min at the temperature of 50-180 ℃, and drying to obtain the prepreg.
The invention also discloses a laminated board, wherein a metal foil is coated on one side or both sides of one prepreg, or at least 2 prepregs are stacked, then the metal foil is coated on one side or both sides of the prepreg, and hot press forming is carried out, so that the laminated board can be obtained.
The preparation steps of the laminated board are as follows: and covering a metal foil on one or two sides of one prepreg, or covering a metal foil on one or two sides of at least 2 prepregs after laminating, and performing hot press forming to obtain the metal foil laminated board. The pressing conditions of the above laminate were: pressing for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.
Specifically, the number of prepregs may be determined according to the thickness of a desired laminate, and one or more prepregs may be used.
The metal foil can be copper foil or aluminum foil, and the material is not limited; the thickness of the metal foil is also not particularly limited, and may be, for example, 5 micrometers, 8 micrometers, 12 micrometers, 18 micrometers, 35 micrometers, or 70 micrometers.
The invention also relates to an insulating panel comprising at least one prepreg as described above.
The invention also discloses an insulating film prepared by adopting the resin composition, the resin composition is dissolved by a solvent to prepare a glue solution, then the glue solution is coated on a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the insulating film.
The invention also provides a high-frequency circuit substrate, which comprises at least one prepreg or/and at least one laminated board or/and at least one insulating film.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention develops a novel modified maleimide compound, and experiments prove that: compared with the existing bismaleimide, the prepreg and the laminated board made of the bismaleimide have the characteristics of excellent dielectric property, heat resistance, high peel strength, low water absorption rate and thermal expansion coefficient, excellent processing technology performance and the like, can be applied to the fields of IC packaging and high speed and high frequency, have wide application prospects, and lay a foundation for better serving the fields of IC packaging and high speed and high frequency;
2. the preparation process of the modified maleimide compound is simple and easy to implement, has low cost and is suitable for popularization and application.
Detailed Description
The invention is further described below with reference to the following examples:
synthesis example 1
A method for preparing a modified maleimide compound, comprising the steps of:
firstly, 300.42g of 2, 2-bis (3-amino-4-hydroxyphenyl) propane, 2L N, N-Dimethylformamide (DMF) and 1L of distilled water are added into a 10L flask with a thermometer, a reflux condenser and a stirring device and are stirred uniformly at 25 ℃; heating the mixture to 60 ℃, slowly adding 296.44g of acetic anhydride dropwise, reacting at the temperature for 2 hours after dropwise addition, and naturally cooling to room temperature after the reaction is finished; filtering and adopting distilled water for multiple times to obtain a solid, and vacuum-drying the obtained solid at 80 ℃ for 10 hours to obtain 360g of a solid reactant (a-1);
secondly, 342.46g of the solid reactant (a-1) and 5L of acetone are added into a 10L flask with a thermometer, a reflux condenser and a stirring device, the mixture is uniformly stirred, 325.2g of p-chloromethyl styrene and 2.8012g of tetra-n-butyl ammonium bromide serving as a catalyst are added, and the mixture is dissolved into 800g of toluene; then slowly heating to 80 ℃, dropwise adding 50% sodium hydroxide aqueous solution within 30 minutes, and reacting for 5 hours at the temperature; after the reaction is finished, neutralizing excessive alkali liquor by using hydrochloric acid with the mass ratio of 10%, and simultaneously adding 1L of methanol to precipitate liquid in the flask; then, the solid obtained was filtered and washed with distilled water several times, and dried under vacuum at 80 ℃ for 5 hours to obtain 406.12g of a solid reactant (b-1);
thirdly, 400.00g of the solid reactant (b-1) and 780ml of ethanol are added into a 10L flask with a thermometer, a reflux condenser and a stirring device, the mixture is stirred uniformly, 400g of concentrated hydrochloric acid is added, the mixture is heated to 70 ℃, the reaction is carried out for 35 hours at the temperature, and the mixture is naturally cooled to the room temperature after the reaction is finished; neutralizing the reaction solution with 30% NaOH aqueous solution, extracting with ethyl acetate 945ml, washing with distilled water for multiple times, adding sodium sulfate, drying, concentrating under reduced pressure, vacuum drying the obtained reactant at 80 ℃ for 10 hours to obtain a liquid reactant, vacuum concentrating the reaction solution to obtain a solid, and vacuum drying the obtained solid at 80 ℃ for 10 hours to obtain 300.0g of a solid reactant (c-1);
fourthly, 152.98g (1.56mol) of maleic anhydride and 4L of toluene are added into a 10L flask with a thermometer, a reflux condenser, a separator and a stirring device; after stirring uniformly, 240g of the solid reactant (c-1) (which is 50% DMF solution after the completion of dropwise addition for 3 hours) is dropwise added, and the reaction is continued for 4 hours at room temperature after the dropwise addition is finished; continuously adding 20g of paratoluenesulfonic acid monohydrate, raising the temperature to 105 ℃, dehydrating at the temperature for 8 hours, cooling and separating water and toluene which are subjected to reflux azeotropy, and returning the toluene to the flask; naturally cooling to room temperature after the dehydration reaction is finished, and carrying out reduced pressure concentration to obtain a brown solution; the brown solution was dissolved in 1600ml of ethyl acetate and washed with distilled water (600ml) and a 2% sodium bicarbonate solution (600ml) 3 times each, dried over sodium sulfate and concentrated under reduced pressure, and the resulting solid was dried under vacuum at 80 ℃ for 10 hours to give a vinylbenzyl-containing bismaleimide compound;
by using1H-NMR(400MHz，CDCl3The obtained solid was analyzed, and a peak at 5 to 7ppm confirmed that the obtained solid was a vinylbenzyl-containing bismaleimide compound (structural formula 9):
Figure GDA0003605250550000091
synthesis example 2
The vinylbenzyl-containing bismaleimide compound (structural formula 10) was obtained in the same manner as in Synthesis example 1 using 5, 5' -methylenebis (2-aminophenol) instead of 2, 2-bis (3-amino-4-hydroxyphenyl) propane, and the vinylbenzyl-containing bismaleimide compound was obtained1H-NMR(400MHz，CDCl3The obtained solid was analyzed, and a peak at 5 to 7ppm confirmed that the obtained solid was a vinylbenzyl-containing bismaleimide compound.
Figure GDA0003605250550000092
Synthesis example 3
The vinylbenzyl-containing bismaleimide compound (structural formula 11) was obtained in the same manner as in Synthesis example 1 using 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane instead of 2, 2-bis (3-amino-4-hydroxyphenyl) propane, and the vinylbenzyl-containing bismaleimide compound was used1H-NMR(400MHz，CDCl3The obtained solid was analyzed, and a peak at 5 to 7ppm confirmed that the obtained solid was a vinylbenzyl-containing bismaleimide compound.
Figure GDA0003605250550000093
Synthesis example 4
The vinylbenzyl-containing bismaleimide compound (structural formula 12) was obtained in the same manner as in Synthesis example 1 using 4,4 '-diamino-3, 3' -dihydroxybiphenyl instead of 2, 2-bis (3-amino-4-hydroxyphenyl) propane, and the resulting product was purified by1H-NMR(400MHz，CDCl3The obtained solid was analyzed, and a peak at 5 to 7ppm confirmed that the obtained solid was a vinylbenzyl-containing bismaleimide compound.
Figure GDA0003605250550000101
Synthesis example 5
The same procedure as in Synthesis example 1 was repeated, except that 5, 5' -methylenebis (2-aminophenol) was used instead of 2, 2-bis (3-amino-4-hydroxyphenyl) propane in the second step, which was different from Synthesis example 1; the second step is as follows: adding reactants A300.00g and acetone 5L into a 10L flask with a thermometer, a reflux condenser and a stirring device, uniformly stirring, then adding 306.826g of sodium carbonate, slowly heating to 90 ℃, reacting for 2 hours at the temperature, and then dropwise adding 233.20g of allyl bromide for 3 hours; after the dropwise addition is finished, continuing the reaction at the temperature for 18 hours, and naturally cooling to room temperature after the reaction is finished; then, the solid was filtered and distilled water was used several times, and the obtained solid was vacuum-dried at 80 ℃ for 5 hours to obtain 367.88g of a solid reactant B; the first, third and fourth steps were the same as in Synthesis example 1, using1H-NMR(400MHz，CDCl3The obtained solid was analyzed, and a peak at 4 to 7ppm confirmed that the obtained solid was a propylene-group-containing bismaleimide compound (structural formula 16).
Figure GDA0003605250550000102
The following E1 to E5 represent examples 1 to 5, respectively; c1 to C4 represent comparative examples 1 to 4, respectively.
E1：
100g of a vinylbenzyl-containing bismaleimide compound (structural formula 9) was dissolved in an appropriate amount of a toluene solvent to prepare a 65% solid content colloidal solution.
The glue solution is dipped and coated on E glass fiber cloth (2116, single weight 104 g/m)2) And drying in an oven at 160 ℃ for 5min to obtain the prepreg with the resin content of 50%.
And placing a metal copper foil on each of the prepregs with the resin content of 50% and placing the prepregs in a vacuum hot press for pressing to obtain the copper-clad plate. The specific pressing process is pressing for 2 hours under the pressure of 1.5Mpa and the temperature of 220 ℃.
The properties of the copper-clad laminate obtained are shown in Table 1.
The glue solution can also be coated on a PET film (G2, Mitsubishi chemical) with the thickness of 10-150 microns and then baked at 50-170 ℃ for 1-10 minutes to obtain an interlayer insulating film (namely an insulating film).
E2：
100g of a vinylbenzyl-containing bismaleimide compound (formula 10) was dissolved in an appropriate amount of toluene solvent to prepare a 65% solids solution.
The preparation methods of the prepreg and the copper-clad laminate are the same as E1.
The properties of the copper-clad laminate obtained are shown in Table 1.
The interlayer insulating film was prepared in the same manner as in E1.
E3：
100g of a vinylbenzyl-containing bismaleimide compound (structural formula 11) was dissolved in an appropriate amount of toluene solvent to prepare a 65% solid content colloidal solution.
The preparation methods of the prepreg and the copper-clad laminate are the same as E1.
The properties of the copper-clad laminate obtained are shown in Table 1.
The interlayer insulating film was prepared in the same manner as in E1.
E4：
100g of a vinylbenzyl-containing bismaleimide compound (structural formula 12) was dissolved in an appropriate amount of a toluene solvent to prepare a 65% solid content gum solution.
The preparation methods of the prepreg and the copper-clad laminate are the same as E1.
The properties of the copper-clad laminate obtained are shown in Table 1.
The interlayer insulating film was prepared in the same manner as in E1.
E5：
100g of a vinylbenzyl-containing bismaleimide compound (formula 13) was dissolved in an appropriate amount of toluene solvent to prepare a 65% solids solution.
The preparation methods of the prepreg and the copper-clad laminate are the same as E1.
The properties of the copper-clad laminate obtained are shown in Table 1.
The interlayer insulating film was prepared in the same manner as in E1.
C1：
100g of 4, 4' -bismaleimidodiphenylmethane (BMI-1 for short, produced by chemical institute in northwest) is dissolved in a proper amount of toluene solvent to prepare a glue solution with 65% of solid content.
The preparation methods of the prepreg and the copper-clad laminate are the same as E1. The properties of the copper-clad laminate obtained are shown in Table 1. The interlayer insulating film was prepared in the same manner as in E1.
C2：
100g of 2, 2-bis [4- (maleimidophenoxy) phenyl ] propane (BMI-2, produced by northwest chemical academy of sciences) was dissolved in a proper amount of toluene solvent to obtain a 65% solids sol.
The preparation methods of the prepreg and the copper-clad laminate are the same as E1. The properties of the copper-clad laminate obtained are shown in Table 1. The interlayer insulating film was prepared in the same manner as in E1.
C3：
100g of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-3, Nippon university, Japan) was dissolved in an appropriate amount of toluene solvent to prepare a 65% solid content gum solution.
The preparation methods of the prepreg and the copper-clad laminate are the same as E1. The properties of the copper-clad laminate obtained are shown in Table 2. The interlayer insulating film was prepared in the same manner as in E1.
C4：
100g of an allyl-containing bismaleimide compound (structural formula 16 obtained in Synthesis example 5) was dissolved in an appropriate amount of a toluene solvent to prepare a 65% solid content dope.
The preparation methods of the prepreg and the copper-clad laminate are the same as E1. The properties of the copper-clad laminate obtained are shown in Table 2. The interlayer insulating film was prepared in the same manner as in E1.
TABLE 1
Figure GDA0003605250550000131
TABLE 2
Figure GDA0003605250550000132
Figure GDA0003605250550000141
Note: table 2 is a continuation of table 1, and the indices are the same, with table 2 added because table 1 is left unreleased.
1) Dielectric constant and dielectric loss: a network analyzer (SPDR) method, with a test frequency of 10 GHz;
2) glass transition temperature (Tg): a dynamic mechanical property tester (TA DMA Q800, USA) is adopted, the heating rate is 10 ℃/min, and the atmosphere is nitrogen;
3) CTE (CTE): testing by adopting a thermal mechanical analysis device (Q400, TA), wherein the temperature is room temperature-350 ℃, the heating rate is 10 ℃/min, the testing is carried out under the protection of nitrogen, the linear expansion coefficient of the surface direction of 50-130 ℃ is measured, and the measuring directions are the longitudinal direction (Y) and the transverse direction (X) of the glass cloth surface;
4) water absorption: taking 3 samples of 10cm multiplied by 10cm with the thickness of 0.80mm and with metal foils removed on two sides, drying at 120 ℃ for 2 hours, then processing at 121 ℃ and 2 atmospheric pressures for 7 hours by using a Pressure Cooker cooking test machine, sucking free water on the surface of the water, putting the water into a dryer for cooling, weighing, and calculating the water absorption of the plate according to the front weight and the rear weight.
From the results of tables 1 and 2, it can be seen that:
c1 in comparison to E2:
c1 has high water absorption (0.70%), high thermal expansion coefficient, high dielectric constant and loss value, and high curing reaction temperature (280 ℃); the invention E2 obviously improves the defects, especially obviously improves the water absorption rate, the peel strength, the dielectric property and the curing reaction temperature.
C2 in comparison to E1:
c2 has the same problems as C1, such as high water absorption, high dielectric constant and high loss value. And E1 further proves that the invention achieves remarkable effect.
C3 vs E4:
the peak temperature of the curing reaction of C3 is high (290 ℃), which shows that the reaction needs higher temperature and longer time, the thermal expansion coefficient is large, the water absorption is high, and the invention E4 achieves remarkable effect.
C4 in comparison to E2:
compared with E2, C4 has a large thermal expansion coefficient, and dielectric properties and peel strength are inferior to those of E2, so that it is significantly insufficient for high-performance printed circuit boards.
In conclusion, the modified maleimide compound and the prepreg and the laminated board manufactured by using the modified maleimide compound have the characteristics of excellent dielectric property, heat resistance, high peel strength, low water absorption rate and thermal expansion coefficient, excellent processing technology performance and the like.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. A modified maleimide compound characterized in that: the chemical structural formula is as follows (1) or (2):
Figure FDA0003660092690000011
wherein: n is 1;
a is a group represented by the following structural formula (3):
Figure FDA0003660092690000012
wherein R is1Represents a hydrogen atom, R2Represents a methylene group;
b is a group represented by the following structural formula (4):
Figure FDA0003660092690000013
wherein R is4、R5Is a hydrogen atom; r6Is a connecting bond to B or X; r3Is a group represented by the following structural formula (5):
Figure FDA0003660092690000014
-O-and R2Connecting; x is-CH2-，-C(CH3)2-，-C(CF3)2-, or-O-.
2. A method for producing the modified maleimide compound according to claim 1, comprising the steps of:
s1: reacting acetic acid or acetic anhydride with a compound with amino to obtain a reactant A;
s2: reacting the reactant A with a compound shown as the following structural formula (a) to obtain a reactant B;
Figure FDA0003660092690000015
wherein R is1Represents a hydrogen atom, R2Represents a methylene group;
s3: reacting the reactant B with ethanol, removing acetic acid and reducing into a reactant C with amino;
s4: subjecting the reactant C to dehydration ring-closure reaction with maleic anhydride to obtain the modified maleimide of claim 1;
the compound with amino is selected from the following structural formula (7) or structural formula (8):
Figure FDA0003660092690000021
y in the structural formula (8) is-CH2-、-C(CH3)2-、-C(CF3)2-or-O-.
3. A resin composition comprising the modified maleimide compound of claim 1 and an additive.
4. The resin composition according to claim 3, characterized in that: the additive is selected from at least one of filler, flame retardant, coupling agent, accelerator, initiator, solvent, pigment and auxiliary agent.
5. A prepreg produced using the resin composition according to claim 3 or 4, characterized in that: dissolving the resin composition with a solvent to prepare a glue solution, then soaking the reinforcing material in the glue solution, and heating and drying the soaked reinforcing material to obtain the prepreg.
6. A laminate, characterized by: the laminate can be obtained by coating a metal foil on one side or both sides of a prepreg according to claim 5, or by laminating at least 2 prepregs according to claim 5, coating a metal foil on one side or both sides, and hot press forming.
7. An insulating board, its characterized in that: comprising at least one prepreg according to claim 5.
8. An insulating film produced from the resin composition according to claim 3 or 4, wherein the resin composition is dissolved in a solvent to prepare a glue solution, the glue solution is applied to a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the insulating film.
9. A high-frequency circuit board comprising at least one prepreg according to claim 5 and/or at least one laminate according to claim 6 and/or at least one insulating sheet according to claim 7 and/or at least one insulating film according to claim 8.
CN202010999594.7A 2020-09-22 2020-09-22 Modified maleimide compound, and prepreg and laminated board manufactured by using same Active CN112079763B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010999594.7A CN112079763B (en) 2020-09-22 2020-09-22 Modified maleimide compound, and prepreg and laminated board manufactured by using same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010999594.7A CN112079763B (en) 2020-09-22 2020-09-22 Modified maleimide compound, and prepreg and laminated board manufactured by using same

Publications (2)

Publication Number Publication Date
CN112079763A CN112079763A (en) 2020-12-15
CN112079763B true CN112079763B (en) 2022-07-05

Family

ID=73739475

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010999594.7A Active CN112079763B (en) 2020-09-22 2020-09-22 Modified maleimide compound, and prepreg and laminated board manufactured by using same

Country Status (1)

Country Link
CN (1) CN112079763B (en)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110088153B (en) * 2016-12-20 2021-03-30 Dic株式会社 Composition, cured product, and laminate
JP2021181505A (en) * 2018-08-22 2021-11-25 昭和電工マテリアルズ株式会社 Resin composition, prepreg, laminate sheet, multilayer printed wiring board, semiconductor package and method for manufacturing multilayer printed wiring board

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Synthesis and Properties of Bismaleimide Resins Containing Ether Bonds;Shinji Takeda et al.;《Journal of Applied Polymer Science》;19881231;第35卷(第5期);第1346页表II *
新型双酚A苯醚型双马来酰亚胺单体制备与性能;吕君君等.;《固体火箭技术》;20110430;第34卷(第2期);第255页表3 *

Also Published As

Publication number Publication date
CN112079763A (en) 2020-12-15

Similar Documents

Publication Publication Date Title
US9867287B2 (en) Low dielectric resin composition with phosphorus-containing flame retardant and preparation method and application thereof
KR101597925B1 (en) Halogen-free resin composition and method for preparatioin of copper clad laminate with same
CN108219371B (en) Epoxy resin composition, prepreg, laminate, and printed wiring board
CN112080102A (en) Resin composition, prepreg, insulating film, metal-clad laminate, and printed wiring board provided with same
EP3037475A1 (en) Phenoxy cyclotriphosphazene active ester, halogen-free resin composition and use thereof
CN110845853B (en) Resin composition, and prepreg, laminated board, insulating board, circuit board and coverlay film comprising same
CN110655775B (en) Resin composition, and prepreg, laminated board and printed wiring board provided with same
CN111393594B (en) Active ester resin and resin composition thereof
CN108148196B (en) Styryl siloxy polyphenylene oxide resin and preparation method and application thereof
CN112062914B (en) Resin composition, prepreg and laminated board prepared from same
CN113121981B (en) Resin composition, prepreg and insulating plate using same
CN110724261B (en) High-heat-resistance low-dielectric polyphenylene ether type bismaleimide resin, laminated board and preparation method thereof
CN108864410B (en) Epoxy resin containing TCPD structure, epoxy resin composition, prepreg, laminated board and printed circuit board
CN108148202B (en) Styryl poly (phenylene ether) resin and preparation method and application thereof
CN110922764B (en) Silicon-containing resin composition and prepreg and laminated board manufactured by using same
CN112079763B (en) Modified maleimide compound, and prepreg and laminated board manufactured by using same
CN110950901B (en) Silicone resin, method for producing the same, resin composition, prepreg, laminated board, insulating board, circuit board, and coverlay film
CN113105498A (en) Halogen-free silicon flame-retardant allyl compound, preparation method thereof and application thereof in copper-clad plate
CN112094480B (en) Resin composition, and prepreg and laminated board manufactured by using same
CN112079722A (en) Active ester compound, resin composition, and prepreg, insulating film, metal-clad laminate, and printed wiring board having the same
CN113462143B (en) Polyphenylene ether resin composition, and prepreg and laminate prepared using the same
CN114316264A (en) Modified bismaleimide prepolymer, resin composition and application thereof
CN113185751A (en) Halogen-free silicon flame-retardant vinyl resin, preparation method thereof and application thereof in copper-clad plate
CN114644824A (en) Flame-retardant polyphenyl ether resin composition, copper-clad plate and preparation method thereof
CN116285378A (en) Resin composition, adhesive sheet containing same, and metal foil-clad laminate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant