WO2021134992A1 - 一种改性马来酰亚胺化合物及其制备方法和应用 - Google Patents

一种改性马来酰亚胺化合物及其制备方法和应用 Download PDF

Info

Publication number
WO2021134992A1
WO2021134992A1 PCT/CN2020/086536 CN2020086536W WO2021134992A1 WO 2021134992 A1 WO2021134992 A1 WO 2021134992A1 CN 2020086536 W CN2020086536 W CN 2020086536W WO 2021134992 A1 WO2021134992 A1 WO 2021134992A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
modified maleimide
maleimide compound
tert
modified
Prior art date
Application number
PCT/CN2020/086536
Other languages
English (en)
French (fr)
Inventor
孟运东
罗成
许永静
方克洪
Original Assignee
广东生益科技股份有限公司
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 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Publication of WO2021134992A1 publication Critical patent/WO2021134992A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2347/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—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
    • C08J2353/02—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2447/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic

Definitions

  • the invention relates to the technical field of printed circuits, in particular to a modified maleimide compound and a preparation method and application thereof.
  • thermosetting polyimide resin maleimide resin has outstanding performance in mechanical properties, electrical properties, heat resistance and solvent resistance.
  • bismaleimide resin or polymaleimide resin has been widely used in the field of packaging substrates.
  • the maleimide resin has been insufficient in terms of adhesion. Therefore, it is generally used in combination with epoxy resins, phenolic resins and cyanate resins with better adhesion.
  • bismaleimide is combined with a lower polar resin, its adhesion performance is still poor.
  • CN106700549A discloses a modified bismaleimide resin, a reinforced laminate and a preparation method thereof.
  • the bismaleimide resin is modified by cyanate ester resin, rubber, dicyandiamide, and silicon dioxide.
  • the bismaleimide resin uses modified bismaleimide resin as the adhesive and glass fiber as the base material to prepare a reinforced laminate through dipping and gluing, tape drying, and lamination.
  • the advantage of the invention is that it provides a modified bismaleimide resin that can meet the requirements of industrial production.
  • a reinforced laminate made of this modified bismaleimide resin and glass fiber is not only good Heat resistance, its mechanical properties have also been significantly improved, excellent comprehensive performance, can be used in electrical insulation, aerospace and other fields. However, in this invention, the obtained laminate still has the problem of high dielectric constant and dielectric loss.
  • CN105295048A discloses a liquid modified bismaleimide resin with high heat resistance and a preparation method thereof. 3-aminobenzocyclobutene and bismaleimide monomer are melted and copolymerized by Michael addition to form a pre After the polymer is cooled, an active diluent is added for heat preservation, and after cooling, a solution containing a catalyst is added, mixed uniformly, and the solvent for dissolving the catalyst is vacuum evaporated to obtain a liquid modified bismaleimide resin with high heat resistance.
  • the resin system provided by the invention presents a flowing liquid state at room temperature. It is a rare species in the field of double-horse resins. It exhibits good processing technology and is suitable for a variety of current composite material molding processes.
  • the composition of the bismaleimide resin and the low-polarity resin of the present invention has poor adhesion to materials such as copper foil and glass fiber cloth, and the resulting laminate has low peel strength.
  • CN101824148A discloses a bismaleimide-triazine resin containing octavinyl cage silsesquioxane and a preparation method thereof.
  • 100 parts of bismaleimide was slowly added to O,O'-diallyl bisphenol A at 120-140°C to obtain prepolymer I; slowly 1894 parts of octaethylene
  • the base cage silsesquioxane is added to prepolymer I at 120 ⁇ 140°C to obtain prepolymer II; weigh 215 ⁇ 280 parts of cyanate ester, slowly add it to prepolymer II, and raise the temperature to 140 ⁇ 160°C, and then keep heat and stir for 1 ⁇ 2 hours to obtain a bismaleimide-triazine resin containing octavinyl cage silsesquioxane.
  • the prepared resin can be used as a basic material for preparing high-performance copper clad laminates in the electronic information field. However, the adhesiveness of the resin is poor, and
  • One of the objectives of the present invention is to provide a modified maleimide compound to improve the bonding performance of the combination with a low-polar resin, and to prepare a laminate with high peel strength, low dielectric and high heat resistance.
  • the present invention adopts the following technical solutions:
  • the present invention provides a modified maleimide compound consisting of compound (A) or an organometallic salt containing amino silane, and containing at least two maleimide groups
  • the compound (B) is prepared, and the molecular structure of the compound (A) is as follows:
  • R 1 , R 2 and R 3 are each independently selected from C1 to C6 (e.g. C1, C2, C3, C4, C5 or C6) alkyl groups;
  • Y is -Y 1 -Y 2 -or
  • the Y 1 and Y 2 are each independently selected from -CH 2 -, -C 2 H 4 -, -C 3 H 6 -, -C 4 H 8 -, -C 5 H 10 -, -C 3 H 6 -N-, -C 2 H 4 -N-, Any of
  • the Y 3 is selected from -H, -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H 11 , -C 8 H 17 , -C 15 H 31 , Any of
  • the m is 0 or 1.
  • a compound (B) containing at least two maleimide groups is heated to react with an amino-containing silane compound (A) or an organometallic salt of amino-containing silane to obtain a modified maleic containing silane Imide compound.
  • an amino-containing silane compound (A) or an organometallic salt of amino-containing silane to obtain a modified maleic containing silane Imide compound.
  • it When it is used in the resin composition of composite materials, it has better compatibility with low-polarity resins, avoids the volatilization of the silane coupling agent during the drying process of the prepreg, and can reduce the bismaleimide
  • the reactivity between amine and other resins reduces the curing stress of the resin composition, increases the adhesion of the resin composition to the reinforcing material or the conductive layer, and maintains low dielectric loss and high heat resistance.
  • the N atom of the compound (A) or the organometallic salt of aminosilane is connected to the ortho position of the carbonyl group in the compound (B), which can exemplarily form a modified maleimide compound with the following structure:
  • the above structure only expresses the connection method after the reaction of the compound (A) or the organometallic salt of aminosilane and the compound (B), and is not limited to the above structure.
  • the obtained modified maleimide compound The structure will also be different.
  • the compound (A) has any one of the following structures shown in formula I to formula III:
  • the R 1 , R 2 , R 3 , Y 1 , Y 2 and Y 3 all have the same selection range as above.
  • the R 1 , R 2 and R 3 are each independently selected from any one of CH 3 , C 2 H 5 or C 3 H 7.
  • the Y 1 and Y 2 are each independently selected from Any of them.
  • the preferred compound (A) of the present invention contains the above-mentioned linking groups. These linking groups can extend the chain length, avoid the influence of the crosslinked structure of the resin after curing on the siloxane, and can further improve the bonding performance of the resin. In addition, these structures The main chain has higher rigidity, which is conducive to high heat resistance.
  • the compound (B) has the structure shown in the following formula IV or formula V:
  • the X is selected from -CH 2 -, -C 2 H 4 -, -C 3 H 6 -, -C 4 H 8 -, -C 5 H 10 -, Any of
  • the R, R 4 to R 11 are each independently selected from -H, C1 to C15 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, etc. )alkyl, Any one of -H, -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H 11 , -C 8 H 17 , -C 15 H 31 , Any of
  • n is an integer of 1-10, such as 2, 3, 4, 5, 6, 7, 8, 9 and the like.
  • the second object of the present invention is to provide a method for preparing the modified maleimide compound according to the first object, the preparation method comprising: compound (A) or an organometallic salt containing aminosilane and containing at least two The compound (B) having one maleimide group undergoes a heating reaction to obtain the modified maleimide compound.
  • the temperature of the heating reaction is 100-200°C, preferably 110°C, 120°C, 130°C, 136°C, 141°C, 145°C, 151°C, 156°C, 160°C, 165°C and 170°C.
  • the heating reaction time is 1-30h, preferably 2h, 3h, 4h, 5h, 6h, 7h, 8h, 10h, 12h, 16h, 21h, 28h.
  • the heating reaction is carried out under the condition of refluxing.
  • the heating reaction is carried out under stirring.
  • the molar ratio of the compound (A) or the organometallic salt containing aminosilane to the compound (B) is 10:90 to 80:20, such as 10:90, 15:85, 20:80, 24:76 , 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, etc.
  • the molar ratio is 30:70-50:50, such as 30:70, 35:65, 38:62, 40:60, 45 :55, 50:50, etc.
  • an accelerator is added in the heating reaction.
  • the amount of the accelerator is 0.01-10% of the mass of compound (B), such as 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.
  • the accelerator includes dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxide isopropyl carbonate, 2,5-dimethyl-2,5 -Di-tert-butylcumylperoxyhexyne-3, 2,5-dimethyl 2,5-di-tert-butylperoxyhexane, p-menthane peroxide, 1,1-bis(tert-pentyl Peroxy) cyclohexane, diisopropylbenzene hydrogen peroxide, benzoyl peroxide, benzoyl peroxide derivatives, metal salts of acetylacetone, metal salts of naphthenic acid, vanadium pentoxide, amine compounds , Quaternary ammonium salt, imidazole, triphenylphosphine, or triphenylphosphine derivative, or any one or a
  • a solvent is added during the heating reaction.
  • the amount of the solvent is 10-500% of the mass of the compound (B), such as 50%, 100%, 150%, 200%, 250%, 300%, 350%, 400%, 450%, 480% Etc., preferably 50-400%;
  • the solvent includes any one or a combination of at least two of toluene, xylene, cyclohexane, tetrahydrofuran, N,N-dimethylformamide (DMF) or methyl ethyl ketone.
  • the third object of the present invention is to provide a resin composition containing the modified maleimide compound described in 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 according to the third object attached to it after being dried by impregnation.
  • the reinforcing material includes glass fiber cloth.
  • the fifth object of the present invention is to provide an insulating board comprising at least one prepreg sheet described in the fourth object.
  • the sixth object of the present invention is to provide a metal-clad laminate, the metal-clad laminate comprising at least one of the prepregs described in the fourth object and one side or two of the laminated prepregs. Metal foil on the side.
  • the seventh object of the present invention is to provide a printed circuit board comprising at least one prepreg according to object four, or at least one insulating board according to object five, or at least one The metal-clad laminate described in the sixth objective.
  • the present invention has the following beneficial effects:
  • a compound (B) containing at least two maleimide groups is heated to react with an amino-containing silane compound (A) or an organometallic salt of amino-containing silane to obtain a silane-containing modified maleic Imide compound.
  • an amino-containing silane compound (A) or an organometallic salt of amino-containing silane to obtain a silane-containing modified maleic Imide compound.
  • it When it is used in the resin composition of composite materials, it has better compatibility with low-polarity resins, avoids the volatilization of the silane coupling agent during the drying process of the prepreg, and can reduce the bismaleimide
  • the reactivity between amine and other resins reduces the curing stress of the resin composition, increases the adhesion of the resin composition to the reinforcing material or the conductive layer, and maintains low dielectric loss and high heat resistance.
  • KBM-602 N-2-( ⁇ -aminoethyl)-3- ⁇ -aminopropylmethyldimethoxysilane, Shin-Etsu;
  • KBM-603 N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, Shin-Etsu;
  • KBM-903 3-Aminopropyltrimethoxysilane, Shin-Etsu Japan;
  • KBE-903 3-Aminopropyltriethoxysilane, Shin-Etsu Japan;
  • KBM-403 3-Glycidyloxypropylmethyltrimethoxysilane, Shin-Etsu Japan;
  • DDM Diaminodiphenylmethane, Attu, India
  • BMI-50P Multifunctional maleimide resin, Japan KI;
  • BMI-70 Bis(3-ethyl-5-methyl-4-maleimidobenzene)methane, Japan KI;
  • BMI-80 2,2-bis(4-(4-maleimidephenoxy)phenyl)propane, Japan KI.
  • Synthesis examples 1 to 6 provide modified maleimide compounds, and the preparation steps are as follows:
  • Amino-containing silane compounds KBM-602, KBM-603, KBM-903, KBE-903
  • compounds containing at least two maleimide groups BMI-70, BMI-80, BMI-50P
  • the accelerator and the solvent are added to a reaction vessel with reflux, stirring and heating. After heating and stirring to reflux, the solvent in the reactant is evaporated and cooled to room temperature to obtain modified maleimide compounds P1 to P6.
  • This synthesis example provides a modified maleimide compound P7 to P10, and the preparation method is as follows:
  • Examples 1 to 10 and Comparative Examples 1 to 2 respectively provide a resin glue solution and laminate.
  • the specific preparation process is as follows:
  • Glass transition temperature Tg use dynamic thermomechanical analysis (DMA) test, refer to the DMA test method specified in IPC-TM-6502.4.24.
  • Td Thermal decomposition temperature
  • Peel strength refers to the tensile force required to peel off the copper clad laminate per millimeter of copper foil at room temperature.
  • V-0 is recognized as flame retardant.
  • OPE-2St Mitsubishi Gas, double-end olefin functionalized polyphenylene ether
  • Ricon257 American Kreweller, butadiene-styrene-divinylbenzene branched terpolymer
  • A1536 American Kraton, SEBS resin
  • Bt-93W American Albemarle, decabromodiphenyl ethylene, flame retardant
  • OP935 American Klein, phosphorus-containing flame retardant
  • DCP Dicumyl peroxide, initiator.
  • the peel strength is greater 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 greater than 190°C
  • the thermal decomposition temperature is greater than 400°C
  • 50 ⁇ The thermal expansion ratio at 260°C is less than 2%
  • the thermal stress is greater than 60min.
  • Comparative Example 1 did not pre-polymerize the amino-containing silane compound and maleimide, but added them to the resin glue separately.
  • the final laminate has higher peel strength, lower Tg and Td, and Dk and Df. Higher, the coefficient of thermal expansion and expansion ratio are larger, and the heat resistance is obviously reduced. This is because during the curing process of the glue, the amino-containing silane compound volatilizes quickly, and the curing reaction between bismaleimide and the olefin resin is relatively fast, thereby reducing the above-mentioned performance.
  • the preparation raw materials of the modified maleimide compound used in Comparative Example 2 also include diallyl phenyl compounds. Compared with the examples, the dielectric properties are significantly reduced, and the dielectric constant and dielectric loss are obvious. High, this is because the reaction of the diallyl phenyl compound and bismaleimide is more complicated, which has an adverse effect on the dielectric properties.
  • the present invention uses the above-mentioned embodiments to illustrate the detailed methods of the present invention, but the present invention is not limited to the above-mentioned detailed methods, which does not mean that the present invention must rely on the above-mentioned detailed methods to be implemented.
  • Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Reinforced Plastic Materials (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

本发明涉及一种改性马来酰亚胺化合物及其制备方法和应用，所述改性马来酰亚胺化合物由化合物(A)或者含氨基硅烷的有机金属盐，以及含有至少两个马来酰亚胺基团的化合物(B)制备。本发明将含有至少两个马来酰亚胺基团的化合物(B)与含氨基的硅烷化合物(A)或者含氨基硅烷的有机金属盐进行预聚，得到一种含硅烷的改性马来酰亚胺化合物，将其用于复合材料的树脂组合物时，其具有与低极性树脂更好的相容性，并在半固化片的烘干过程中避免硅烷偶联剂的挥发，并能降低双马来酰亚胺与其他树脂之间反应性，使树脂组合物的固化应力降低，增加树脂组合物对增强材料或导电层之间的粘合力，并保持低介电损耗和高耐热性。

Description

一种改性马来酰亚胺化合物及其制备方法和应用 技术领域
本发明涉及印制电路技术领域，尤其涉及一种改性马来酰亚胺化合物及其制备方法和应用。
背景技术
随着电子电气行业的进步和终端电子的迅猛发展，电子线路基板的发展方向为轻薄化、高性能化、高可靠性以及环保等。马来酰亚胺树脂作为一种热固性聚酰亚胺树脂，在力学性能、电性能、耐热性和耐溶剂性能方面均有着卓越的表现。在电子电路基板中，双马来酰亚胺树脂或多马来酰亚胺树脂目前已在封装基板领域有了大量的应用。但目前存在的问题之一为马来酰亚胺树脂在粘合力方面一直表现不足，因此，一般将其与粘结性较好的环氧树脂、酚醛树脂和氰酸酯树脂进行组合使用，但是将双马来酰亚胺与极性较低树脂进行组合时，其粘结性表现仍很差。
CN106700549A公开了一种改性双马来酰亚胺树脂、增强层压板及其制备方法，双马来酰亚胺树脂经氰酸酯树脂、橡胶、双氰胺、二氧化硅改性得到改性双马来酰亚胺树脂，以改性双马来酰亚胺树脂为胶黏剂，以玻璃纤维为基材，经过浸涂上胶、胶布干燥、层压制备得到增强层压板。该发明的优点是，提供了一种能够满足工业生产要求的改性双马来酰亚胺树脂以这种改性双马来酰亚胺树脂与玻璃纤维制备的增强层压板，不仅具有良好的耐热性能，其力学性能也得到了显著的提高，综合性能优良，可应用于电气绝缘、航空航天等领域。但是该发明中，得到的层压板仍会存在介电常数和介电损耗较高的问题。
CN105295048A公开了一种高耐热性液体改性双马来酰亚胺树脂及其制备方法，将3-氨基苯并环丁烯与双马来酰亚胺单体经迈克尔加成熔融共聚形成预聚体，降温后添加活性稀释剂保温，冷却后加入溶有催化剂的溶液，混合均匀，真空蒸除溶解催化剂的溶剂，得到高耐热性液态改性双马来酰亚胺树脂。该发明提供的树脂体系常温下呈现流动液态，是双马树脂领域不多见的品种，表现出良好的加工工艺性，适合目前多种复合材料成型工艺，不仅可用作高级覆铜板的基础树脂，而且还可以用于航空航天、交通运输等领域的先进复合材料或耐高温胶黏剂等。但是该发明的双马来酰亚胺树脂与低极性树脂组成的组合物与铜箔、玻璃纤维布等材料的粘结性较差，制备得到的层压板的剥离强度低。
CN101824148A公开了一种含八乙烯基笼型倍半硅氧烷的双马来酰亚胺-三嗪树脂及其制备方法。按重量计，在120～140℃下，将100份双马来酰亚胺缓慢加入到O,O'-二烯丙基双酚A中，得到预聚体I；缓慢地将1894份八乙烯基笼型倍半硅氧烷加入到120～140℃的预聚体I中，得到预聚体II；称取215～280份的氰酸酯，缓慢加入到预聚体II中，升温至140～160℃，再保温搅拌1～2小时，得到一种含八乙烯基笼型倍半硅氧烷的双马来酰亚胺-三嗪树脂。制得的树脂可作为电子信息领域制备高性能覆铜板等的基础材料。但是该树脂的粘结性较差，制备得到的覆铜板的剥离强度较低。
因此，本领域亟待开发一种新型的马来酰亚胺化合物，改善与低极性树脂组合的粘结性能，且得到低介电和高耐热的层压板。
发明内容
本发明的目的之一在于提供改性马来酰亚胺化合物，改善与低极性树脂组合的粘结性能，进而制备得到高剥离强度、低介电和高耐热性的层压板。
为达此目的，本发明采用以下技术方案：
本发明提供一种改性马来酰亚胺化合物，所述改性马来酰亚胺化合物由化合物(A)或者含氨基硅烷的有机金属盐，以及含有至少两个马来酰亚胺基团的化合物(B)制备，所述化合物(A)的分子结构如下：
Figure PCTCN2020086536-appb-000001
所述R 1、R 2和R 3各自独立地选自C1～C6(例如C1、C2、C3、C4、C5或C6)烷基；
所述Y的结构为-Y 1-Y 2-或
Figure PCTCN2020086536-appb-000002
所述Y 1和Y 2各自独立地选自-CH 2-、-C 2H 4-、-C 3H 6-、-C 4H 8-、-C 5H 10-、-C 3H 6-N-、-C 2H 4-N-、
Figure PCTCN2020086536-appb-000003
Figure PCTCN2020086536-appb-000004
Figure PCTCN2020086536-appb-000005
中的任意一种；
所述Y 3选自-H、-CH 3、-C 2H 5、-C 3H 7、-C 4H 9、-C 5H 11、-C 8H 17、-C 15H 31、
Figure PCTCN2020086536-appb-000006
Figure PCTCN2020086536-appb-000007
中的任意一种；
所述m为0或1。
本发明将含有至少两个马来酰亚胺基团的化合物(B)与含氨基的硅烷化合物(A)或者含氨基硅烷的有机金属盐进行加热反应，得到一种含硅烷的改性马来酰亚胺化合物。将其用于复合材料的树脂组合物时，其具有与低极性树脂更 好的相容性，并在半固化片的烘干过程中避免硅烷偶联剂的挥发，并能降低双马来酰亚胺与其他树脂之间反应性，使树脂组合物的固化应力降低，增加树脂组合物对增强材料或导电层之间的粘合力，并保持低介电损耗和高耐热性。
本发明中，化合物(A)或者氨基硅烷的有机金属盐的N原子与化合物(B)中羰基邻位连接，示例性地可以形成如下结构的改性马来酰亚胺化合物：
Figure PCTCN2020086536-appb-000008
上述结构仅为了表述化合物(A)或氨基硅烷的有机金属盐和化合物(B)反应后的连接方式，并不限于上述结构，根据原料结构的不同，得到的改性马来酰亚胺化合物的结构也会有所不同。
优选地，所述化合物(A)具有如下式I至式III所示的结构中的任意一种：
Figure PCTCN2020086536-appb-000009
Figure PCTCN2020086536-appb-000010
所述R 1、R 2、R 3、Y 1、Y 2和Y 3均具有与前文相同的选择范围。
优选地，所述R 1、R 2和R 3各自独立地选自CH 3、C 2H 5或C 3H 7中的任意一种。
优选地，所述Y 1和Y 2各自独立地选自
Figure PCTCN2020086536-appb-000011
Figure PCTCN2020086536-appb-000012
Figure PCTCN2020086536-appb-000013
中的任意一种。
本发明优选化合物(A)中包含上述连接基团，这些连接基团能够延长链长度，避免树脂固化后的交联结构对硅氧烷的影响，能够进一步提升树脂的粘结性能，另外这些结构的主链具有更高的刚性，有利于高耐热性。
优选地，所述化合物(B)具有如下式IV或式V所示的结构：
Figure PCTCN2020086536-appb-000014
所述X选自-CH 2-、-C 2H 4-、-C 3H 6-、-C 4H 8-、-C 5H 10-、
Figure PCTCN2020086536-appb-000015
Figure PCTCN2020086536-appb-000016
Figure PCTCN2020086536-appb-000017
中的任意一种；
所述R、R 4～R 11各自独立地选自-H、C1～C15(例如C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14等)烷基、
Figure PCTCN2020086536-appb-000018
中的任意一种，优选-H、-CH 3、-C 2H 5、-C 3H 7、-C 4H 9、-C 5H 11、-C 8H 17、-C 15H 31、
Figure PCTCN2020086536-appb-000019
中的任意一种；
所述n为1～10的整数，例如2、3、4、5、6、7、8、9等。
本发明的目的之二在于提供一种目的之一所述的改性马来酰亚胺化合物的制备方法，所述制备方法包括：化合物(A)或者含氨基硅烷的有机金属盐与含有至少两个马来酰亚胺基团的化合物(B)进行加热反应，得到所述改性马来酰亚胺化合物。
优选地，所述加热反应的温度为100～200℃，优选110℃、120℃、130℃、136℃、141℃、145℃、151℃、156℃、160℃、165℃和170℃。
优选地，所述加热反应的时间为1～30h，优选2h、3h、4h、5h、6h、7h、8h、10h、12h、16h、21h、28h。
优选地，所述加热反应在冷凝回流的条件下进行。
优选地，所述加热反应在搅拌下进行。
优选地，所述化合物(A)或者含氨基硅烷的有机金属盐与化合物(B)的摩尔比为10:90～80:20，例如10:90、15:85、20:80、24:76、30:70、40:60、50:50、60:40、70:30、80:20等。为了使化合物(A)与化合物(B)能够充分的发生反 应，进一步优选地，摩尔比为30:70～50:50，例如30:70、35:65、38:62、40:60、45:55、50:50等。
优选地，所述加热反应中加入促进剂。
优选地，所述促进剂的用量为化合物(B)质量的0.01～10％，例如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％等。
优选地，所述促进剂包括过氧化二枯基、叔丁基过氧化枯基、过氧化二叔丁基、过氧化异丙基碳酸叔丁酯、2,5-二甲基-2,5-二叔丁基枯基过氧基己炔-3、2,5-二甲基2,5-二叔丁基过氧化己烷、过氧化对孟烷、1,1-双(叔戊基过氧)环己烷、过氧化氢二异丙基苯、过氧化苯甲酰、过氧化苯甲酰衍生物、乙酰丙酮的金属盐、环烷酸的金属盐、五氧化钒、胺类化合物、季铵盐、咪唑、三苯基膦或三苯基膦衍生物中的任意一种或至少两种组合。
优选地，所述加热反应中加入溶剂。
优选地，所述溶剂的用量为化合物(B)质量的10～500％，例如50％、100％、150％、200％、250％、300％、350％、400％、450％、480％等，优选50～400％；
优选地，所述溶剂包括甲苯、二甲苯、环己烷、四氢呋喃、N,N-二甲基甲酰胺(DMF)或丁酮中的任意一种或至少两种组合。
本发明的目的之三在于提供一种树脂组合物，所述树脂组合物中含有目的之一所述的改性马来酰亚胺化合物。
本发明的目的之四在于提供一种预浸片，所述预浸片包括增强材料及通过含浸干燥后附着其上的目的之三所述的树脂组合物。
优选地，所述增强材料包括玻璃纤维布。
本发明的目的之五在于提供一种绝缘板，所述绝缘板包括至少一张目的之 四述的预浸片。
本发明的目的之六在于提供一种覆金属箔层压板，所述覆金属箔层压板包括至少一张目的之四所述的预浸片以及覆于叠合后的预浸片一侧或两侧的金属箔。
本发明的目的之七在于提供一种印刷电路板，所述印刷电路板包括至少一张目的之四所述的预浸片，或至少一张目的之五所述的绝缘板，或至少一张目的之六所述的覆金属箔层压板。
相对于现有技术，本发明具有以下有益效果：
本发明将含有至少两个马来酰亚胺基团的化合物(B)与含氨基的硅烷化合物(A)或者含氨基硅烷的有机金属盐进行加热反应，得到一种含硅烷的改性马来酰亚胺化合物。将其用于复合材料的树脂组合物时，其具有与低极性树脂更好的相容性，并在半固化片的烘干过程中避免硅烷偶联剂的挥发，并能降低双马来酰亚胺与其他树脂之间反应性，使树脂组合物的固化应力降低，增加树脂组合物对增强材料或导电层之间的粘合力，并保持低介电损耗和高耐热性。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
下文所涉及到的化合物的详细信息如下：
KBM-602：N-2-(β-氨乙基)-3-γ-氨丙基甲基二甲氧基硅烷，日本信越；
KBM-603：N-2-(氨乙基)-3-氨丙基三甲氧基硅烷，日本信越；
KBM-903：3-氨丙基三甲氧基硅烷，日本信越；
KBE-903：3-氨丙基三乙氧基硅烷，日本信越；
1,2-乙二胺，N,N'-双苄基-N-[3-(三甲氧基硅烷)丙基]-盐酸盐，CAS： 145151-33-3，试剂，市售；
KBM-403：3-缩水基甘油醚氧基丙基甲基三甲氧基硅烷，日本信越；
DDM：二氨基二苯甲烷，印度阿图；
DDS：二氨基二苯砜，印度阿图；
CAS：92-87-5，4,4'-二氨基联苯，试剂，市售；
BMI-50P：多官能马来酰亚胺树脂，日本KI；
BMI-70：双(3-乙基-5-甲基-4-马来酰亚胺基苯)甲烷，日本KI；
BMI-80：2,2-二(4-(4-马来酰亚胺苯氧基)苯基)丙烷，日本KI。
合成例1～6
合成例1～6提供种改性马来酰亚胺化合物，制备步骤如下：
将含氨基的硅烷化合物(KBM-602，KBM-603，KBM-903，KBE-903)、含有至少两个马来酰亚胺基团的化合物(BMI-70，BMI-80，BMI-50P)、促进剂和溶剂加入具有冷凝回流、搅拌和加热的反应容器中，加热搅拌回流后，蒸出反应物中的溶剂，冷却至常温，得到改性马来酰亚胺化合物P1～P6。
合成例1～6的原料组成、反应时间和反应温度详见表1。
表1
Figure PCTCN2020086536-appb-000020
Figure PCTCN2020086536-appb-000021
表1中，——代表不添加对应物质。
合成例7～10
本合成例提供一种改性马来酰亚胺化合物P7～P10，其制备方法如下：
将KBM-403、二胺化合物(DDM、DDS或4,4'-二氨基联苯)和DMF加入具有冷凝回流，搅拌和加热的反应容器中，加热至160℃搅拌回流2h，然后加入含有两个以上马来酰亚胺基团的化合物(BMI-70或BMI-50P)，加热搅拌回流后，蒸出反应物中的溶剂，冷却至常温，得到改性马来酰亚胺化合物P7～10。
合成例7～10的原料组成、反应时间和反应温度详见表2。
表2
  合成例7 合成例8 合成例9 合成例10
  P7 P8 P9 P10
KBM-403 6 50 45 50
DDM —— —— —— 30
DDS —— —— 35 ——
4,4'-二氨基联苯 4 30 —— ——
BMI-70 90   20 20
BMI-50P —— 20 —— ——
DMF 100   10 20
MEK —— 20 —— ——
三苯基膦 —— —— 0.2 0.2
反应温度 100℃ 150℃ 200℃ 160℃
反应时间 30h 5h 1h 10h
表2中，——代表不添加对应物质。
对比合成例1
按照专利申请CN101775139A的实施例1制备得到的改性双马来酰亚胺树脂(D1)，具体步骤如下：
将100份双马来酰亚胺、50份二烯丙基苯基化合物、12份γ氨丙基三乙氧基硅烷及0.50～1.50份水在室温下混合在温度为40℃的条件下反应60分钟；再升温至150C，预聚反应120分钟后，得到一种改性双马来酰亚胺树脂D1。
实施例1～10、对比例1～2
实施例1～10、对比例1～2分别提供一种树脂胶液及层压板，具体制备过程如下：
(1)树脂胶液的制备：
先将改性马来酰亚胺化合物(P1～P10、D1中的一种)或未改性的马来酰亚胺化合物在DMF中溶解，然后与配方中的其他组分混合均匀，即得到树脂胶液；具体配方详见表3；
(2)层压板的制备：
取型号为2116的玻璃纤维布均匀浸渍上述树脂胶液，在鼓风烘箱中于155℃烘烤5min制得预浸片，将6张上述预浸片重叠，上下覆35μm反转铜箔，于真空热压机中在3MPa压力和220℃温度下压制90min得到层压板。
性能测试：
(1)玻璃化转变温度Tg：使用动态热机械分析(DMA)测试，参考IPC-TM-6502.4.24所规定的DMA测试方法。
(2)热分解温度(Td)：使用热失重分析(TGA)测试，参考标准IPC-TM-650 2.4.24.6。
(3)剥离强度(PS)：指在室温下将每毫米铜箔剥离覆铜板所需的拉力。
(4)介电常数(Dk)和介电损耗因数(Df)：使用平板电容法测定，参考标准IPC-TM-650 2.4.24
(5)阻燃：按照UL94“50W(20mm)垂直燃烧试验：V-0、V-1和V-2” 测试方法测试，认定V-0为阻燃。
(6)热膨胀系数和50～260℃热膨胀比例：测试采用静态热分析仪(TMA)测试，测试参考标准IPC-TM-650 2.4.24。
(7)热应力：将带铜的层压板漂浮在熔融状态的锡液表面，温度288℃，以分层或气泡的时间作为测试结果。
上述测试结果详见表3。
表3
Figure PCTCN2020086536-appb-000022
Figure PCTCN2020086536-appb-000023
Figure PCTCN2020086536-appb-000024
表3中各组分的详细信息如下：
OPE-2St：三菱瓦斯，双端烯烃官能化聚苯醚；
B-1000：日本曹达，聚丁二烯树脂；
Ricon257：美国克雷威勒，丁二烯-苯乙烯-二乙烯基苯枝化三元共聚物；
A1536：美国科腾，SEBS树脂；
NQ1025J：无机填料NQ1025J球型熔融二氧化硅，D50＝3.0μm，江苏联瑞新材料股份有限公司；
Bt-93W：美国雅宝，十溴二苯乙撑，阻燃剂；
OP935：美国克莱恩，含磷阻燃剂；
DCP：过氧化二异丙苯，引发剂。
——代表不添加对应物质。
由表3可知，本发明提供的改性马来酰亚胺化合物与低极性树脂组合后，具有较强的粘结性能，制备得到的层压板具有较高的剥离强度，同时具有良好的介电性能和耐热性能，其中，剥离强度为大于0.8N/mm，1GHz介电常数小于3.8，1GHz介电损耗因数小于0.002，玻璃化转变温度大于190℃，热分解温度大于400℃，50～260℃热膨胀比例小于2％，热应力均大于60min。
对比例1没有将含有氨基的硅烷化合物与马来酰亚胺进行预聚，而是分别加入至树脂胶液中，最终得到的层压板的剥离强度较高，Tg和Td较低，Dk和Df较高，热膨胀系数和膨胀比例较大，耐热性能明显下降。这是由于，在胶液固化的过程中，含有氨基的硅烷化合物快速挥发，而且双马来酰亚胺与烯烃树 脂的固化反应较快，进而使上述性能降低。
对比例2中所使用的改性马来酰亚胺化合物的制备原料中还包括二烯丙基苯基化合物，与实施例相比，其介电性能明显降低，介电常数和介电损耗明显偏高，这是由于二烯丙基苯基化合物与双马来酰亚胺的反应比较复杂，对介电性能造成了不利影响。
本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种改性马来酰亚胺化合物，其特征在于，所述改性马来酰亚胺化合物由化合物(A)或者含氨基硅烷的有机金属盐，以及含有至少两个马来酰亚胺基团的化合物(B)制备，所述化合物(A)的分子结构如下：
    Figure PCTCN2020086536-appb-100001
    所述R 1、R 2和R 3各自独立地选自C1～C6烷基；
    所述Y的结构为——Y 1-Y 2——或
    Figure PCTCN2020086536-appb-100002
    所述Y 1和Y 2各自独立地选自-CH 2-、-C 2H 4-、-C 3H 6-、-C 4H 8-、-C 5H 10-、-C 3H 6-N-、-C 2H 4-N-、
    Figure PCTCN2020086536-appb-100003
    Figure PCTCN2020086536-appb-100004
    Figure PCTCN2020086536-appb-100005
    中的任意一种；
    所述Y 3选自-H、-CH 3、-C 2H 5、-C 3H 7、-C 4H 9、-C 5H 11、-C 8H 17、-C 15H 31、
    Figure PCTCN2020086536-appb-100006
    Figure PCTCN2020086536-appb-100007
    中的任意一种；
    所述m为0或1。
  2. 根据权利要求1所述的改性马来酰亚胺化合物，其特征在于，所述化合物(A)具有如下式I至式III所示的结构中的任意一种：
    Figure PCTCN2020086536-appb-100008
    所述R 1、R 2、R 3、Y 1、Y 2和Y 3均具有与权利要求1相同的限定范围。
  3. 根据权利要求1或2所述的改性马来酰亚胺化合物，其特征在于，所述R 1、R 2和R 3各自独立地选自CH 3、C 2H 5或C 3H 7中的任意一种；
    优选地，所述Y 1和Y 2各自独立地选自
    Figure PCTCN2020086536-appb-100009
    Figure PCTCN2020086536-appb-100010
    Figure PCTCN2020086536-appb-100011
    中的任意一种。
  4. 根据权利要求1～3中任一项所述的改性马来酰亚胺化合物，其特征在于，所述化合物(B)具有如下式IV或式V所示的结构：
    Figure PCTCN2020086536-appb-100012
    所述X选自-CH 2-、-C 2H 4-、-C 3H 6-、-C 4H 8-、-C 5H 10-、
    Figure PCTCN2020086536-appb-100013
    Figure PCTCN2020086536-appb-100014
    Figure PCTCN2020086536-appb-100015
    中的任意一种；
    所述R、R 4～R 11各自独立地选自-H、C1～C15烷基、
    Figure PCTCN2020086536-appb-100016
    Figure PCTCN2020086536-appb-100017
    中的任意一种，优选-H、-CH 3、-C 2H 5、-C 3H 7、-C 4H 9、-C 5H 11、-C 8H 17、-C 15H 31、
    Figure PCTCN2020086536-appb-100018
    中的任意一种；
    所述n为1～10的整数。
  5. 一种根据权利要求1～4中任一项所述的改性马来酰亚胺化合物的制备方法，其特征在于，所述制备方法包括：化合物(A)或者含氨基硅烷的有机金属盐与含有至少两个马来酰亚胺基团的化合物(B)进行加热反应，得到所述改性马来酰亚胺化合物；
    优选地，所述加热反应的温度为100～200℃；
    优选地，所述加热反应的时间为1～30h；
    优选地，所述加热反应在冷凝回流的条件下进行；
    优选地，所述加热反应在搅拌下进行；
    优选地，所述化合物(A)或者含氨基硅烷的有机金属盐与化合物(B)的摩尔比为10:90～80:20；
    优选地，所述加热反应中加入促进剂；
    优选地，所述促进剂的用量为化合物(B)质量的0.01～10％；
    优选地，所述促进剂包括过氧化二枯基、叔丁基过氧化枯基、过氧化二叔丁基、过氧化异丙基碳酸叔丁酯、2,5-二甲基-2,5-二叔丁基枯基过氧基己炔-3、2,5-二甲基2,5-二叔丁基过氧化己烷、过氧化对孟烷、1,1-双(叔戊基过氧)环己烷、过氧化氢二异丙基苯、过氧化苯甲酰、过氧化苯甲酰衍生物、乙酰丙酮的金属盐、环烷酸的金属盐、五氧化钒、胺类化合物、季铵盐、咪唑、三苯基膦或三苯基膦衍生物中的任意一种或至少两种组合；
    优选地，所述加热反应中加入溶剂；
    优选地，所述溶剂的用量为化合物(B)质量的10～500％，优选50～400％；
    优选地，所述溶剂包括甲苯、二甲苯、环己烷、四氢呋喃、N,N-二甲基甲酰胺或丁酮中的任意一种或至少两种组合。
  6. 一种树脂组合物，其特征在于，所述树脂组合物中含有权利要求1～4中任一项所述的改性马来酰亚胺化合物。
  7. 一种预浸片，其特征在于，所述预浸片包括增强材料及通过含浸干燥后附着其上的权利要求6所述的树脂组合物；
    优选地，所述增强材料包括玻璃纤维布。
  8. 一种绝缘板，其特征在于，所述绝缘板包括至少一张权利要求7所述的预浸片。
  9. 一种覆金属箔层压板，其特征在于，所述覆金属箔层压板包括至少一张权利要求7所述的预浸片以及覆于叠合后的预浸片一侧或两侧的金属箔。
  10. 一种印刷电路板，其特征在于，所述印刷电路板包括至少一张权利要求7所述的预浸片，或至少一张权利要求8所述的绝缘板，或至少一张权利要求9所述的覆金属箔层压板。
PCT/CN2020/086536 2019-12-31 2020-04-24 一种改性马来酰亚胺化合物及其制备方法和应用 WO2021134992A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201911421022.4A CN113121586A (zh) 2019-12-31 2019-12-31 一种改性马来酰亚胺化合物及其制备方法和应用
CN201911421022.4 2019-12-31

Publications (1)

Publication Number Publication Date
WO2021134992A1 true WO2021134992A1 (zh) 2021-07-08

Family

ID=76686877

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/086536 WO2021134992A1 (zh) 2019-12-31 2020-04-24 一种改性马来酰亚胺化合物及其制备方法和应用

Country Status (3)

Country Link
CN (1) CN113121586A (zh)
TW (1) TWI756679B (zh)
WO (1) WO2021134992A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114015046A (zh) * 2021-12-07 2022-02-08 苏州生益科技有限公司 一种改性双马来酰亚胺预聚物及使用其制备的组合物、半固化片及其压层板
CN114605825A (zh) * 2022-04-11 2022-06-10 焦作市天益科技有限公司 一种感光防静电复合材料及其制备方法
CN117024659A (zh) * 2023-09-11 2023-11-10 河南大树实业有限公司 一种大粒径高固含量丁苯胶乳的制备方法
CN117024659B (zh) * 2023-09-11 2024-05-31 河南大树实业有限公司 一种大粒径高固含量丁苯胶乳的制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113512057B (zh) * 2021-07-20 2022-09-20 山东阳谷华泰化工股份有限公司 一种双马来酰亚胺丙基二乙氧基硅烷及其制备方法和用途
CN114561101A (zh) * 2022-04-01 2022-05-31 焦作市天益科技有限公司 一种可延长保质期的二烯丙基双酚a改性双马来酰亚胺树脂及制备方法
KR20240052716A (ko) * 2022-10-11 2024-04-23 셍기 테크놀로지 (쑤저우) 컴퍼니 리미티드 개질된 비스말레이미드 프리폴리머, 수지 조성물 및 수지 조성물의 용도
CN116120560B (zh) * 2022-10-11 2024-04-12 苏州生益科技有限公司 改性双马来酰亚胺预聚物的制备方法、树脂组合物及树脂组合物的应用

Citations (3)

* 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
CN106916418A (zh) * 2015-12-25 2017-07-04 广东生益科技股份有限公司 一种热固性树脂组合物、半固化片、覆金属箔层压板以及印制电路板
CN110317541A (zh) * 2019-06-19 2019-10-11 南亚新材料科技股份有限公司 一种粘结片以及高速覆铜板的制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002128957A (ja) * 2000-10-24 2002-05-09 Yokohama Rubber Co Ltd:The 老化防止剤及びそれを含むゴム組成物
EP2468759A1 (de) * 2010-12-17 2012-06-27 Sika Technology AG Sekundäre Aminosilane
CN102584886A (zh) * 2012-01-17 2012-07-18 华南理工大学 一种硅烷偶联剂及其制备方法
CN102775605A (zh) * 2012-08-14 2012-11-14 西北工业大学 一种改性双马来酰亚胺树脂及其制备方法
CN104845363B (zh) * 2014-02-14 2017-04-05 广东生益科技股份有限公司 一种无卤树脂组合物及其用途
CN109879903A (zh) * 2019-01-09 2019-06-14 青岛科技大学 一种新型防老硅烷偶联剂及其制备方法
CN110218415B (zh) * 2019-05-31 2021-07-06 广东生益科技股份有限公司 树脂组合物、预浸料、层压板、覆金属箔层压板以及印刷线路板
CN113088061B (zh) * 2019-12-23 2022-11-29 广东生益科技股份有限公司 一种热固性树脂组合物及使用其的预浸料、层压板和覆金属箔层压板

Patent Citations (3)

* 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
CN106916418A (zh) * 2015-12-25 2017-07-04 广东生益科技股份有限公司 一种热固性树脂组合物、半固化片、覆金属箔层压板以及印制电路板
CN110317541A (zh) * 2019-06-19 2019-10-11 南亚新材料科技股份有限公司 一种粘结片以及高速覆铜板的制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GAMBOGI JOAN E., BLUM FRANK D.: "Molecular mobility of the interface in a model polymer composite: a NMR study", MACROMOLECULES, AMERICAN CHEMICAL SOCIETY, WASHINGTON DC UNITED STATES, vol. 25, no. 18, 1 August 1992 (1992-08-01), Washington DC United States, pages 4526 - 4534, XP055826457, ISSN: 0024-9297, DOI: 10.1021/ma00044a011 *
TAMAMI B., ET AL.: "SYNTHESIS AND APPLICATION OF ABRASION RESISTANT COATING MATERIALS BASED ON FUNCTIONALIZED BIS AND TRIS MALEIMIDES.", POLYMER BULLETIN, SPRINGER, HEIDELBERG., DE, vol. 30., no. 04., 1 April 1993 (1993-04-01), DE, pages 393 - 399., XP000363554, ISSN: 0170-0839, DOI: 10.1007/BF00338471 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114015046A (zh) * 2021-12-07 2022-02-08 苏州生益科技有限公司 一种改性双马来酰亚胺预聚物及使用其制备的组合物、半固化片及其压层板
CN114015046B (zh) * 2021-12-07 2023-11-10 苏州生益科技有限公司 一种改性双马来酰亚胺预聚物及使用其制备的组合物、半固化片及其层压板
CN114605825A (zh) * 2022-04-11 2022-06-10 焦作市天益科技有限公司 一种感光防静电复合材料及其制备方法
CN117024659A (zh) * 2023-09-11 2023-11-10 河南大树实业有限公司 一种大粒径高固含量丁苯胶乳的制备方法
CN117024659B (zh) * 2023-09-11 2024-05-31 河南大树实业有限公司 一种大粒径高固含量丁苯胶乳的制备方法

Also Published As

Publication number Publication date
TWI756679B (zh) 2022-03-01
TW202126726A (zh) 2021-07-16
CN113121586A (zh) 2021-07-16

Similar Documents

Publication Publication Date Title
TWI756679B (zh) 一種改性馬來醯亞胺化合物及其製備方法及應用
US9867287B2 (en) Low dielectric resin composition with phosphorus-containing flame retardant and preparation method and application thereof
US9872382B2 (en) Low dielectric composite material and laminate and printed circuit board thereof
CN107254144B (zh) 树脂组合物和使用其的预浸料以及层压板
US9629239B2 (en) Resin composition, and prepreg as well as laminate using the same
WO2020155291A1 (zh) 一种热固性树脂组合物、包含其的预浸料以及覆金属箔层压板和印制电路板
CN103131130B (zh) 环氧树脂组成物及应用其的低介电常数绝缘材料
CN109337289B (zh) 热固性树脂组合物及含有它的预浸料、层压板和高频电路基板
CN109988298B (zh) 一种改性聚苯醚树脂、热固性树脂组合物及其用途
TW201506081A (zh) 低介電樹脂組合物及應用其之銅箔基板及印刷電路板
WO2015188377A1 (zh) 一种苯氧基环三磷腈活性酯、无卤树脂组合物及其用途
WO2016074288A1 (zh) 一种热固性树脂组合物及用其制作的预浸料与层压板
EP2706091A1 (en) Epoxy resin composition, and prepreg and copper clad laminate made therefrom
US20150114693A1 (en) Insulating resin composition for printed circuit board and products manufactured by using the same
CN111793327A (zh) 一种高速高频覆铜板用环氧树脂组合物及其制备方法
TWI742643B (zh) 一種樹脂組合物以及使用其的預浸片及絕緣板
CN109971175B (zh) 改性马来酰亚胺树脂组合物及其制备的半固化片和层压板
CN109608828B (zh) 一种热固性树脂组合物及使用其的预浸料、层压板和覆金属箔层压板
JP4317380B2 (ja) 変性ポリイミド樹脂組成物ならびにそれを用いたプリプレグおよび積層板
CN114605779A (zh) 一种热固性树脂组合物及包含其的预浸料、电路基板和印刷电路板
CN112824451B (zh) 低介电树脂组合物、半固化片、及覆铜层压板
CN110452545B (zh) 树脂组合物、印刷电路用预浸片及覆金属层压板
TWI753194B (zh) 樹脂組合物、印刷電路用預浸片及覆金屬層壓板
CN111378136B (zh) 活性酯树脂及其制备方法、热固性树脂组合物、半固化片、绝缘薄膜、层压板和印刷电路板
CN109694462B (zh) 一种热固性树脂组合物及使用其的预浸料、覆金属箔层压板和印制电路板

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20910184

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20910184

Country of ref document: EP

Kind code of ref document: A1