WO2024050891A1 - 苯并噁嗪树脂、制备方法及胶粘剂 - Google Patents

苯并噁嗪树脂、制备方法及胶粘剂 Download PDF

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WO2024050891A1
WO2024050891A1 PCT/CN2022/121715 CN2022121715W WO2024050891A1 WO 2024050891 A1 WO2024050891 A1 WO 2024050891A1 CN 2022121715 W CN2022121715 W CN 2022121715W WO 2024050891 A1 WO2024050891 A1 WO 2024050891A1
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benzoxazine resin
preparation
group
primary amine
adhesive
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PCT/CN2022/121715
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English (en)
French (fr)
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王宏远
张翼蓝
潘瑞
王和志
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瑞声科技（南京）有限公司
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Priority to US18/090,531 priority Critical patent/US20240101746A1/en
Publication of WO2024050891A1 publication Critical patent/WO2024050891A1/zh

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    • 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
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08G73/02—Polyamines
    • C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C09J161/14—Modified phenol-aldehyde condensates
    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
    • 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
    • C09J179/00—Adhesives based on 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 C09J161/00 - C09J177/00
    • C09J179/02—Polyamines
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C08G2170/00—Compositions for adhesives
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/163—Metal in the substrate
    • 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
    • C09J2461/00—Presence of condensation polymers of aldehydes or ketones

Definitions

  • the invention belongs to the technical field of electronic glue, and in particular relates to a benzoxazine resin, a preparation method and an adhesive.
  • dihydroxy-substituted phthalimide monomers, aldehydes, and primary amines are usually used as reactants to synthesize benzoxazine intermediates containing phthalimide structures, thereby obtaining imide group-containing benzoxazine intermediates.
  • Benzoxazine resin Although the resin has good heat resistance, the cured product has poor bending resistance and dielectric properties, and cannot meet the bending resistance requirements of flexible copper-clad laminates.
  • an adhesive material composed of one or more substances selected from polyisocyanate, melamine and silane-modified epoxy resin. This material has a low dielectric constant and low dielectric loss tangent and has good heat resistance. sex.
  • the curing temperature of this product is relatively high, which can easily lead to oxidation of the copper foil when preparing copper-clad laminates.
  • carbon dioxide is released during the curing process of isocyanates and acid anhydrides, which can easily lead to defects such as pores after the product is cured, resulting in printed circuit board explosions during soldering.
  • the purpose of the present invention is to provide a benzoxazine resin to solve the problem that existing adhesive materials composed of benzoxazine resin cannot meet the needs of new high-frequency flexible copper-clad laminates.
  • the present invention provides a benzoxazine resin, the molecular formula of the benzoxazine resin is as follows:
  • R 1 , R 2 , R 3 and R 4 are independently selected from -H and alkyl, alkoxy, cycloalkyl and aromatic groups, and at least one of them is -H;
  • X 1 is the main chain Or the side chain contains an alkyl group or/and an alkoxy group with a long chain structure; or more, the number n of the imide group repeating units is between 1 and 150.
  • the number n of the imide group repeating units is between 20 and 100.
  • the number of carbon atoms included in the alkyl group and the alkoxy group is between 5 and 30.
  • embodiments of the present invention also provide a preparation method of benzoxazine resin, which preparation method includes the following steps:
  • the primary amine-terminated flexible polyimide oligomer is a product of tetracarboxylic dianhydride and a dibasic primary amine, the main chain or side chain of the dibasic primary amine contains a flexible long-chain diamine. or mixtures with other aromatic diamines.
  • the aldehyde compound is formaldehyde and/or paraformaldehyde.
  • the monofunctional phenolic compound has the following molecular formula:
  • R 5 , R 6 , R 7 and R 8 are each independently selected from -H, alkyl, alkoxy, cycloalkyl and aromatic groups, and one or more of the groups is -H.
  • the number of carbon atoms in the alkyl group and the cycloalkyl group is between 1 and 10.
  • the preparation method also includes: adding a solvent, the solvent is toluene, xylene, dioxane, tetrahydrofuran, methanol, ethanol, acetone, methyl ethyl ketone, cyclohexanone, N,N-dimethylmethane.
  • a solvent is toluene, xylene, dioxane, tetrahydrofuran, methanol, ethanol, acetone, methyl ethyl ketone, cyclohexanone, N,N-dimethylmethane.
  • a mixture of one or more of amide, N,N-dimethylacetamide and N-methylpyrrolidone is amide, N,N-dimethylacetamide and N-methylpyrrolidone.
  • the reaction temperature is 60°C-180°C, and the reaction time is 0.5h-10h.
  • the preparation method of the primary amine-terminated flexible polyimide oligomer includes the following steps:
  • the molar ratio of the tetracarboxylic dianhydride component and the dibasic primary amine component is 1 ⁇ (dibasic primary amine/tetracarboxylic dianhydride) ⁇ 1.1.
  • the first preset temperature is -20°C-30°C
  • the first preset time is 0.5h-24h.
  • the tetracarboxylic dianhydride is 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 4,4'-diphenyl ether dianhydride, 3,3',4,4'- One or more of benzophenone tetracarboxylic dianhydride, hexafluoro dianhydride, bisphenol A diether dianhydride and pyromellitic anhydride.
  • the molecular formula of the diamine whose main chain or side chain contains a flexible long chain is as follows:
  • X 3 contains an alkyl group or/and alkoxy group with a long chain structure in the main chain or side chain;
  • the aromatic diamines are m-phenylenediamine, 4,4-diaminodiphenyl ether, p-phenylenediamine, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- One or more of aminophenoxy)benzene and 1,4-bis(4-aminophenoxy)benzene.
  • the molar ratio of the diamine containing a flexible long chain to the aromatic diamine in the main chain or side chain is 2:8-10:0.
  • the molecular weight of the primary amine-terminated flexible polyimide oligomer is Mn1000-100000.
  • embodiments of the present invention also provide an adhesive, which includes a benzoxazine resin prepared by any of the above-mentioned benzoxazine resin preparation methods.
  • the adhesive is applied to film-like adhesive materials, adhesive layers, adhesive sheets, resin-coated copper foil, copper-clad laminates and resin multi-layer substrates.
  • the benzoxazine resin in the present invention is synthesized by using primary amine-terminated flexible polyimide oligomers, aldehyde compounds and monofunctional phenolic compounds as reactants.
  • the synthesized main chain contains
  • the long-chain benzoxazine resin of flexible polyimide can undergo ring-opening polymerization under heating conditions and does not release small molecules during the curing process. After curing, it can be produced with low media properties. Electric constant and dielectric loss, and can meet the requirements of high-frequency flexible copper-clad laminate adhesiveness, soldering resistance, etc., so that the adhesive material composed of it can meet the requirements through the characteristics of benzoxazine resin Demand for high frequency flexible copper clad laminates.
  • Figure 1 is a schematic diagram of the infrared spectrum of Embodiment 4 of the present invention.
  • Figure 2 is a schematic diagram comparing the DMA test storage modulus of Example 4 of the present invention and Comparative Example 1.
  • This embodiment provides a benzoxazine resin, the molecular formula of the benzoxazine resin is as follows:
  • R 1 , R 2 , R 3 and R 4 are independently selected from -H and alkyl, alkoxy, cycloalkyl and aromatic groups, and at least one of them is -H;
  • X 1 is the main chain Or the side chain contains an alkyl group or/and an alkoxy group with a long chain structure; or more, the number n of the imide group repeating units is between 1 and 150.
  • the number n of the imide group repeating units is between 20 and 100.
  • the number of carbon atoms included in the alkoxy group is between 5 and 30.
  • Embodiments of the present invention also provide a preparation method of benzoxazine resin.
  • the preparation method includes the following steps: reacting a primary amine-terminated flexible polyimide oligomer, an aldehyde compound and a monofunctional phenolic compound. It is a synthetic benzoxazine resin containing an imide structure in its main chain.
  • the synthesized benzoxazine resin whose main chain contains a flexible polyimide long chain can undergo ring-opening polymerization under heating conditions and does not release small molecules during the curing process.
  • An adhesive with low dielectric constant and dielectric loss that can meet the requirements of high-frequency flexible copper-clad laminate adhesion and soldering resistance is produced.
  • the primary amine-terminated flexible polyimide oligomer is the product of tetracarboxylic dianhydride and a dibasic primary amine, and the dibasic primary amine contains a flexible long-chain diamine in its main chain or side chain. or mixtures with other aromatic diamines.
  • the aldehyde compound is formaldehyde and/or paraformaldehyde.
  • the monofunctional phenolic compound has the following molecular formula:
  • R 5 , R 6 , R 7 and R 8 are each independently selected from -H, alkyl, alkoxy, cycloalkyl and aromatic groups, and one or more of the groups is -H.
  • the number of carbon atoms in the alkyl group and the cycloalkyl group is between 1 and 10.
  • Preferred aromatic groups are phenyl or alkyl-substituted phenyl; examples of phenyl include phenol, p-methylphenol, m-methylphenol, p-ethylphenol, etc.
  • the preparation method also includes: adding a solvent, the solvent is toluene, xylene, dioxane, tetrahydrofuran, methanol, ethanol, acetone, butanone, cyclohexanone, N,N-dimethyl One or more mixtures of formamide, N,N-dimethylacetamide and N-methylpyrrolidone.
  • the reaction temperature is 60°C-180°C, and the reaction time is 0.5h-10h.
  • the preparation method of the primary amine-terminated flexible polyimide oligomer includes the following steps:
  • the second preset temperature and the second preset time are also set according to the selected compound.
  • the second preset temperature can be -20-30°C, and the second preset time can be 0.5-24h. More preferably, the second preset temperature can be 20°C, and the second preset time can be 15 hours.
  • the molar ratio of the tetracarboxylic dianhydride component and the dibasic primary amine component is 1 ⁇ (dibasic primary amine/tetracarboxylic dianhydride) ⁇ 1.1.
  • the first preset temperature and the first preset time are set according to the selected compound, and are not specifically limited here.
  • the first preset temperature is -20°C-30°C
  • the first preset time is 0.5h-24h. More preferably, the first preset temperature is 10°C, and the first preset time is 12 hours.
  • the tetracarboxylic dianhydride includes 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA), 4,4'-diphenyl ether dianhydride (ODPA); 3,3' , 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), hexafluorodianhydride (6FDA); one of bisphenol A type diether dianhydride (BPADA) and pyromellitic anhydride (PMDA) or Various.
  • BPDA 3,3',4,4'-biphenyl tetracarboxylic dianhydride
  • ODPA 4,4'-diphenyl ether dianhydride
  • BTDA 4,4'-benzophenone tetracarboxylic dianhydride
  • 6FDA hexafluorodianhydride
  • BPADA bisphenol A type diether dianhydride
  • PMDA pyromellitic anhydr
  • the molecular formula of the diamine whose main chain or side chain contains a flexible long chain is as follows:
  • X 3 contains an alkyl group or/and alkoxy group with a long chain structure in the main chain or side chain;
  • the aromatic diamines are m-phenylenediamine, 4,4-diaminodiphenyl ether, p-phenylenediamine, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- One or more of aminophenoxy)benzene and 1,4-bis(4-aminophenoxy)benzene.
  • the molar ratio of the diamine containing a flexible long chain to the aromatic diamine in the main chain or side chain is 2:8-10:0.
  • the molecular weight of the primary amine-terminated flexible polyimide oligomer is Mn1000-100000.
  • the benzoxazine resin in the present invention is synthesized by using primary amine-terminated flexible polyimide oligomers, aldehyde compounds and monofunctional phenolic compounds as reactants.
  • the synthesized main chain contains
  • the long-chain benzoxazine resin of flexible polyimide can undergo ring-opening polymerization under heating conditions and does not release small molecules during the curing process. After curing, it can be produced with low media properties. Electric constant and dielectric loss, and can meet the requirements of high-frequency flexible copper-clad laminate adhesiveness, soldering resistance, etc., so that the adhesive material composed of it can meet the requirements through the characteristics of benzoxazine resin Demand for high frequency flexible copper clad laminates.
  • An embodiment of the present invention also provides an adhesive, which includes the benzoxazine resin prepared by the preparation method of Embodiment 2 above.
  • the adhesive is applied to film-like adhesive materials, adhesive layers, adhesive sheets, resin-coated copper foil, copper-clad laminates and resin multi-layer substrates.
  • the adhesive in this embodiment includes the benzoxazine resin prepared in Example 2, when it is applied to a high-frequency flexible copper-clad laminate, it can meet the performance requirements of the high-frequency flexible copper-clad laminate for adhesive materials.
  • This embodiment provides a method for preparing benzoxazine resin.
  • the specific steps are: under the condition of nitrogen (N 2 ) protection, put 8.4g polyether into a one-neck flask equipped with magnetic stirring and water separator. Amine D400 and 44.01g N-methylpyrrolidone were dissolved. After the dissolution was completed, 10.46g bisphenol A type diether dianhydride (BPADA) was slowly added, and the reaction was carried out at room temperature for 1 hour. The reaction temperature was raised to 140°C and the reaction was carried out for 10 hours to obtain the primary amine.
  • N 2 nitrogen
  • BPADA bisphenol A type diether dianhydride
  • End-capped flexible polyimide oligomer solution after cooling, add 0.095g phenol, 0.06g paraformaldehyde and 0.36g toluene in a single-neck flask, replace the water separator with a condenser tube, heat to 90°C and reflux for 6 hours, react After completion, a yellow transparent liquid with a solid content of 30% is obtained, which is benzoxazine resin.
  • This embodiment provides a preparation method of benzoxazine resin.
  • the specific steps are: under the protection of N2 , put 6.8g of polyetheramine D400 into a single-necked flask equipped with magnetic stirring and water separator. , 4,4-diaminodiphenyl ether (ODA) and 42.15g N-methylpyrrolidone. After dissolution, slowly add 10.46g bisphenol A-type diether dianhydride (BPADA), react at room temperature for 1 hour, and raise the temperature to 140°C.
  • ODA 4,4-diaminodiphenyl ether
  • BPADA bisphenol A-type diether dianhydride
  • This embodiment provides a method for preparing benzoxazine resin.
  • the specific steps are: under N 2 protection, put 4.83g polyetheramine D230 and 35.68g N into a single-necked flask equipped with magnetic stirring and water separator.
  • -Methylpyrrolidone after the dissolution is completed, slowly add 10.46g of bisphenol A-type diether dianhydride (BPADA), react at room temperature for 1 hour, then raise the temperature to 140°C and react for 10 hours to obtain a primary amine-terminated flexible polyimide oligomer.
  • BPADA bisphenol A-type diether dianhydride
  • This embodiment provides a preparation method of benzoxazine resin.
  • the specific steps are: under the protection of N2 , put 11.50g of dimerdiamine 1074 (polyamine 1074) into a single-necked flask equipped with magnetic stirring and water separator.
  • Big smart material priamine 1074) and 51.25g N-methylpyrrolidone after the dissolution is completed, slowly add 10.46g bisphenol A type diether dianhydride (BPADA), react at room temperature for 1 hour, raise the temperature to 140°C and react for 10 hours to obtain the primary amine seal Flexible polyimide oligomer solution at the end; after cooling, add 0.095g phenol, 0.06g paraformaldehyde and 0.36g toluene in a single-neck flask, replace the water separator with a condenser tube, heat to 90°C and reflux for 6 hours, react After completion, a yellow transparent liquid with a solid content of 30% was obtained, thereby obtaining benzoxazine resin.
  • BPADA bisphenol A type diether dianhydride
  • This embodiment provides a method for preparing a flexible polyimide solution.
  • the specific steps are: under nitrogen protection, put 4.01g of 4,4-diaminodiphenyl into a single-neck flask equipped with a magnetic stirrer and a water separator.
  • Ether and 33.77g N-methylpyrrolidone after the dissolution is completed, slowly add 10.46g bisphenol A-type diether dianhydride (BPADA), react at room temperature for 1 hour, then raise the temperature to 140°C and react for 10 hours to obtain a flexible polyethylene with a solid content of 30%.
  • BPADA bisphenol A-type diether dianhydride
  • This embodiment provides a method for preparing an adhesive sheet.
  • the specific steps are: taking the compositions prepared in Examples 4 to 7 and Comparative Example 1, and coating the adhesive solution on the corona-passed PI substrate, respectively.
  • the copper foil is separately pressed and solidified to prepare a copper-clad single-sided panel.
  • the side with the adhesive is pressed and solidified to prepare a multi-layer substrate.
  • the specific tests are as follows:
  • the equipment used to calculate the average value is an electronic universal testing machine.
  • Examples 4 to 7 and Comparative Example 1 were applied to PTFE with a film thickness of 50u after curing, dried and cured at 220°C for 20 minutes and then peeled off to obtain a sample for dielectric measurement with a film thickness of about 50um according to IPC-TM. -650-2.5.5.10 Test specification, use a commercially available dielectric constant test device (cavity resonator type, manufactured by AET) to test the dielectric constant and dielectric loss tangent at 10GHz.
  • a commercially available dielectric constant test device cavity resonator type, manufactured by AET
  • the equipment is TA Company's DMA850, and the tensile mode is used during testing.
  • Example 4-1 the copper-clad laminates prepared based on Examples 4 to 7 are respectively used as Example 4-1 and Example 5.
  • Example 6-1, Example 7-1, and the copper-clad laminate prepared based on Comparative Example 1 is used as Comparative Example 1-1.
  • Example 4-1 The performance test results of Example 4-1 to Example 7-1 and Comparative Example 1-1 are shown in Table 2 below:
  • Figure 1 is the infrared absorption spectrum of the sample prepared in Example 4.
  • imide absorption peaks appear at 1775cm-1, 1718cm-1, 1370cm-1, and tiny oxazine appears at 920cm-1
  • the ring characteristic absorption peak indicates the synthesis of benzoxazine containing imide structure.
  • Figure 2 is a comparison of the change of DMA storage modulus with temperature between Example 4 and Comparative Example 1. It can be clearly seen from Figure 2 that the adhesive for copper-clad laminates with low dielectric loss provided by the present invention is better than ordinary adhesives. The adhesive has better heat resistance.
  • Example 4-1 to Example 7-1 are better than those of Comparative Example 1-1, which illustrates that the low dielectric loss copper-clad laminate provided by the embodiment of the present invention is used
  • the adhesive has better bonding properties and lower dielectric constant and loss.

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Abstract

一种苯并噁嗪树脂、制备方法及胶粘剂，苯并噁嗪树脂的分子式(I)如下,其中，R 1、R 2、R 3、R 4分别独立的选自-H和烷基、烷氧基、环烷基和芳香基，且其中至少一个基团为-H；X 1为主链或侧链含有长链结构的烷基或/和烷氧基；X 2为单键的烷基、醚基、烷氧基、烷基酯基、羰基、砜基以及硫醚基中的一种或多种，酰亚胺基团重复单元的数目n在1-150之间。上述苯并噁嗪树脂具备低介电常数和介电损耗，且能够满足高频挠性覆铜板粘接性，耐锡焊等需求。

Description

苯并噁嗪树脂、制备方法及胶粘剂 【技术领域】
本发明属于电子胶技术领域，尤其涉及一种苯并噁嗪树脂、制备方法及胶粘剂。
【背景技术】
随着信息科技的发展，电子传输速度已向着高频及高速化发展，电子产品则向着多功能化、多密度化及多层次化发展，挠性印刷电路板越来越多的应用在电子设备中，其性能受到了越来越高的挑战。
相关技术中，通常以双羟基取代的酞酰亚胺单体，醛类，伯胺为反应物，合成含有酞酰亚胺结构的苯并噁嗪中间体，进而得到含酰亚胺基团的苯并噁嗪树脂。虽然该树脂的耐热性好，但固化物的耐弯折性能和介电性能较差，无法满足挠性覆铜板耐弯折性能要求。或者选自由多异氰酸酯、三聚三胺和硅烷改性环氧树脂的一种以上物质组成的胶粘材料，该材料具有低的介电常数和低介质损耗角正切，同时具有较好的耐热性。然而该产品固化温度较高，制备覆铜板时易导致铜箔氧化，且异氰酸酯与酸酐固化过程中会释放二氧化碳，易导致产品固化后出现气孔等缺陷，导致印刷线路板锡焊时发生爆板。
因此，实有必要提供一种新的苯并噁嗪树脂、制备方法及胶粘剂解决上述的技术问题。
【发明内容】
本发明的目的在于如何提供一种苯并噁嗪树脂，以解决现有苯并噁嗪树脂组成的胶粘材料已无法满足新型高频挠性覆铜板的需求的问题。
第一方面，本发明提供了一种苯并噁嗪树脂，所述苯并噁嗪树脂的分子式如下：
Figure PCTCN2022121715-appb-000001
其中，R 1、R 2、R 3、R 4分别独立的选自-H和烷基、烷氧基、环烷基和芳香基，且其中至少一个基团为-H；X 1为主链或侧链含有长链结构的烷基或/和烷氧基；X 2为单键的烷基、醚基、烷氧基、烷基酯基、羰基、砜基以及硫醚基中的一种或多种，酰亚胺基团重复单元的数目n在1-150之间。
优选的，所述酰亚胺基团重复单元的数目n在20-100之间。
优选的，所述烷基和所述烷氧基中包括碳原子数为5-30之间。
第二方面，本发明实施例还提供一种苯并噁嗪树脂的制备方法，所述制备方法包括以下步骤：
以伯胺封端的柔性聚酰亚胺齐聚物、醛类化合物和单官能酚类化合物为反应物，合成主链含有酰亚胺结构的苯并噁嗪树脂。
优选的，所述伯胺封端的柔性聚酰亚胺齐聚物为四羧酸二酐与二元伯胺的产物，所述二元伯胺为主链或侧链含有柔性长链的二胺或其与其他芳香族二胺的混合物。
优选的，所述醛类化合物为甲醛和/或多聚甲醛。
优选的，所述单官能酚类化合物具有如下结构的分子式：
Figure PCTCN2022121715-appb-000002
其中，R 5、R 6、R 7、R 8分别独立的选自-H、烷基、烷氧基、环烷基和 芳香基，且其中一个或多个的基团为-H。
优选的，所述烷基和所述环烷基中碳原子数为1-10之间。
优选的，所述反应物的摩尔比为伯胺封端的柔性聚酰亚胺齐聚物：醛类化合物：单官能酚类化合物＝(0.8-1.2)：(1.6-2.5)：(0.9-1.3)。
优选的，所述制备方法还包括：加入溶剂，所述溶剂为甲苯、二甲苯、二氧六环、四氢呋喃、甲醇、乙醇、丙酮、丁酮、环己酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和N-甲基吡咯烷酮中的一种或多种的混合物。
优选的，所述反应物在反应过程中，反应温度为60℃-180℃，反应时间为0.5h-10h。
优选的，所述伯胺封端的柔性聚酰亚胺齐聚物的制备方法包括以下步骤：
S1、在氮气的保护的条件下，将所述二元伯胺溶解在所述溶剂中形成第一混合溶剂；
S2、往所述第一混合溶剂中逐步加入所述四羧酸二酐；
S3、通过在第一预设温度的条件下，持续反应第一预设时间以得到第二混合溶剂；
S4、往所述第二混合溶剂中加入催化剂或带水剂，并使其在第二预设温度的条件下，亚胺化处理第二预设时间，之后析出或干燥后得到所述伯胺封端的柔性聚酰亚胺齐聚物。
优选的，所述四羧酸二酐成分与所述二元伯胺成分的摩尔数的比率为1≤(二元伯胺/四羧酸二酐)＜1.1。
优选的，所述第一预设温度为-20℃-30℃，所述第一预设时间为0.5h-24h。
优选的，所述四羧酸二酐为3,3’,4,4’-联苯四羧酸二酐、4,4’-联苯醚二酐、3,3’,4,4’-二苯酮四酸二酐、六氟二酐、双酚A型二醚二酐和均苯四甲酸酐中的一种或多种。
优选的，所述主链或侧链含有柔性长链的二胺的分子式如下：
H 2N——X 3——NH 2；
其中，X 3为主链或侧链含有长链结构的烷基或/和烷氧基；
所述芳香族二胺为间苯二胺、4，4-二氨基二苯醚、对苯二胺、1，3-双(3-氨基苯氧基)苯、1，3-双(4-氨基苯氧基)苯和1，4-双(4-氨基苯氧基)苯中的一种或多种。
优选的，所述主链或侧链含有柔性长链的二胺与芳香族二胺摩尔比为2:8-10:0。
优选的，所述伯胺封端的柔性聚酰亚胺齐聚物的分子量为Mn1000-100000。
第三方面，本发明实施例还提供一种胶粘剂，所述胶粘剂包括上述任意一项所述的苯并噁嗪树脂的制备方法制得的苯并噁嗪树脂。
优选的，所述胶粘剂应用于膜状胶粘材料、胶粘层、胶粘片、带树脂的铜箔、覆铜箔层压板以及树脂多层基板。
与现有技术相比，本发明中的苯并噁嗪树脂通过以伯胺封端的柔性聚酰亚胺齐聚物、醛类化合物和单官能酚类化合物为反应物合成，合成的主链含有柔性聚酰亚胺长链的苯并噁嗪树脂，利用苯并噁嗪在加热条件下即可发生开环聚合，且固化过程中不释放小分子的特点，固化后即可制得具备低介电常数和介电损耗，且能够满足高频挠性覆铜板粘接性，耐锡焊等要求的粘接剂，从而可以通过苯并噁嗪树脂的特性，使其组成的胶粘材料能满足高频挠性覆铜板的需求。
【附图说明】
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图，其中：
图1为本发明实施例四的红外图谱示意图；
图2为本发明实施例四与对比例一的DMA测试储能模量比较示意图。
【具体实施方式】
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图 及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例一
本实施例提供了一种苯并噁嗪树脂，所述苯并噁嗪树脂的分子式如下：
Figure PCTCN2022121715-appb-000003
其中，R 1、R 2、R 3、R 4分别独立的选自-H和烷基、烷氧基、环烷基和芳香基，且其中至少一个基团为-H；X 1为主链或侧链含有长链结构的烷基或/和烷氧基；X 2为单键的烷基、醚基、烷氧基、烷基酯基、羰基、砜基以及硫醚基中的一种或多种，酰亚胺基团重复单元的数目n在1-150之间。
优选的，所述酰亚胺基团重复单元的数目n在20-100之间。
优选的，所述烷氧基中包括碳原子数为5-30之间。
实施例二
本发明实施例还提供一种苯并噁嗪树脂的制备方法，所述制备方法包括以下步骤：以伯胺封端的柔性聚酰亚胺齐聚物、醛类化合物和单官能酚类化合物为反应物，合成主链含有酰亚胺结构的苯并噁嗪树脂。合成的主链含有柔性聚酰亚胺长链的苯并噁嗪树脂，利用苯并噁嗪在加热条件下即可发生开环聚合，且固化过程中不释放小分子的特点，固化后即可制得具备低介电常数和介电损耗，且能够满足高频挠性覆铜板粘接性，耐锡焊等要求的粘接剂。
具体的，所述伯胺封端的柔性聚酰亚胺齐聚物为四羧酸二酐与二元伯胺的产物，所述二元伯胺为主链或侧链含有柔性长链的二胺或其与其他芳香族二胺的混合物。
具体的，所述醛类化合物为甲醛和/或多聚甲醛。
具体的，所述单官能酚类化合物具有如下结构的分子式：
Figure PCTCN2022121715-appb-000004
其中，R 5、R 6、R 7、R 8分别独立的选自-H、烷基、烷氧基、环烷基和芳香基，且其中一个或多个的基团为-H。
更优的，所述烷基和所述环烷基中碳原子数为1-10之间。优选的芳香基为苯基或烷基取代的苯基；苯基可列举为苯酚，对甲基苯酚，间甲基苯酚，对乙基苯酚等。
具体的，所述反应物的摩尔比为伯胺封端的柔性聚酰亚胺齐聚物：醛类化合物：单官能酚类化合物＝(0.8-1.2)：(1.6-2.5)：(0.9-1.3)。
更优的，所述制备方法还包括：加入溶剂，所述溶剂为甲苯、二甲苯、二氧六环、四氢呋喃、甲醇、乙醇、丙酮、丁酮、环己酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和N-甲基吡咯烷酮中的一种或多种的混合物。
具体的，所述反应物在反应过程中，反应温度为60℃-180℃，反应时间为0.5h-10h。
更优的，所述伯胺封端的柔性聚酰亚胺齐聚物的制备方法包括以下步骤：
S1、在氮气的保护的条件下，将所述二元伯胺溶解在所述溶剂中形成第一混合溶剂。
S2、往所述第一混合溶剂中逐步加入所述四羧酸二酐。
S3、通过在第一预设温度的条件下，持续反应第一预设时间以得到第二混合溶剂。
S4、往所述第二混合溶剂中加入催化剂或带水剂，并使其在第二预设温度的条件下，亚胺化处理第二预设时间，之后析出或干燥后得到所述伯 胺封端的柔性聚酰亚胺齐聚物。
其中，第二预设温度和第二预设时间也根据选取的化合物进行设定，可选的，第二预设温度可以为-20-30℃，第二预设时间可以为0.5-24h。更优的，第二预设温度可以为20℃，第二预设时间可以为15h。
更优的，所述四羧酸二酐成分与所述二元伯胺成分的摩尔数的比率为1≤(二元伯胺/四羧酸二酐)＜1.1。
具体的，第一预设温度和第一预设时间根据选取的化合物进行设定，在此不作具体限定。当然，根据实际需求，所述第一预设温度为-20℃-30℃，所述第一预设时间为0.5h-24h。更优的，所述第一预设温度为10℃，所述第一预设时间为12h。
具体的，所述四羧酸二酐包括3,3’,4,4’-联苯四羧酸二酐(BPDA)、4,4，-联苯醚二酐(ODPA)；3,3’,4,4’-二苯酮四酸二酐(BTDA)、六氟二酐(6FDA)；双酚A型二醚二酐(BPADA)和均苯四甲酸酐(PMDA)中的一种或多种。
具体的，所述主链或侧链含有柔性长链的二胺的分子式如下：
H 2N——X 3——NH 2；
其中，X 3为主链或侧链含有长链结构的烷基或/和烷氧基；
所述芳香族二胺为间苯二胺、4，4-二氨基二苯醚、对苯二胺、1，3-双(3-氨基苯氧基)苯、1，3-双(4-氨基苯氧基)苯和1，4-双(4-氨基苯氧基)苯中的一种或多种。
具体的，所述主链或侧链含有柔性长链的二胺与芳香族二胺摩尔比为2:8-10:0。
具体的，所述伯胺封端的柔性聚酰亚胺齐聚物的分子量为Mn1000-100000。
与现有技术相比，本发明中的苯并噁嗪树脂通过以伯胺封端的柔性聚酰亚胺齐聚物、醛类化合物和单官能酚类化合物为反应物合成，合成的主链含有柔性聚酰亚胺长链的苯并噁嗪树脂，利用苯并噁嗪在加热条件下即可发生开环聚合，且固化过程中不释放小分子的特点，固化后即可制得具备低介电常数和介电损耗，且能够满足高频挠性覆铜板粘接性，耐锡焊等 要求的粘接剂，从而可以通过苯并噁嗪树脂的特性，使其组成的胶粘材料能满足高频挠性覆铜板的需求。
实施例三
本发明实施例还提供一种胶粘剂，所述胶粘剂包括上述实施例二制备方法制得的苯并噁嗪树脂。
更优的，所述胶粘剂应用于膜状胶粘材料、胶粘层、胶粘片、带树脂的铜箔、覆铜箔层压板以及树脂多层基板。
由于本实施例中的胶粘剂包括实施例二中制得的苯并噁嗪树脂，因此，其应用于高频挠性覆铜板时，可以满足高频挠性覆铜板对于胶粘材料的性能需求。
实施例四
本实施例提供了一种苯并噁嗪树脂的制备方法，具体步骤为：在氮气(N 2)保护的条件下，在装有磁力搅拌和分水器的单口烧瓶中装入8.4g聚醚胺D400和44.01gN-甲基吡咯烷酮进行溶解，溶解完毕后缓慢加入10.46g双酚A型二醚二酐(BPADA)，在常温下反应1h，将反应温度升温至140℃反应10h，得到伯胺封端的柔性聚酰亚胺齐聚物溶液；冷却后在单口烧瓶中加入0.095g苯酚、0.06g多聚甲醛和0.36g甲苯，将分水器更换为冷凝管，升温至90℃回流6h，反应结束后得到固含量为30％的黄色透明液体，便为苯并噁嗪树脂。
实施例五
本实施例提供了一种苯并噁嗪树脂的制备方法，具体步骤为：在N 2保护下，在装有磁力搅拌和分水器的单口烧瓶中装入6.8g聚醚胺D400，0.8g，4，4-二氨基二苯醚(ODA)和42.15gN-甲基吡咯烷酮，溶解完毕后缓慢加入10.46g双酚A型二醚二酐(BPADA)，在常温下反应1h，升温至140℃反应10h，得到伯胺封端的柔性聚酰亚胺齐聚物溶液；、冷却后在单口烧瓶中加入0.095g苯酚、0.06g多聚甲醛和0.36g甲苯，将分水器更换为冷凝管，升温至90℃回流6h，反应结束后得到固含量为30％的黄色透明液体，从而得到苯并噁嗪树脂。
实施例六
本实施例提供了一种苯并噁嗪树脂的制备方法，具体步骤为：在N 2保护下，在装有磁力搅拌和分水器的单口烧瓶中装入4.83g聚醚胺D230和35.68gN-甲基吡咯烷酮，溶解完毕后缓慢加入10.46g双酚A型二醚二酐(BPADA)，在常温下反应1h，升温至140℃反应10h，得到伯胺封端的柔性聚酰亚胺齐聚物溶液；冷却后在单口烧瓶中加入0.095g苯酚、0.06g多聚甲醛和0.36g甲苯，将分水器更换为冷凝管，升温至90℃回流6h，反应结束后得到固含量为30％的黄色透明液体，从而得到苯并噁嗪树脂。
实施例七
本实施例提供了一种苯并噁嗪树脂的制备方法，具体步骤为：在N 2保护下，在装有磁力搅拌和分水器的单口烧瓶中装入11.50g二聚二胺1074(禾大智能材料priamine 1074)和51.25gN-甲基吡咯烷酮，溶解完毕后缓慢加入10.46g双酚A型二醚二酐(BPADA)，在常温下反应1h，升温至140℃反应10h，得到伯胺封端的柔性聚酰亚胺齐聚物溶液；、冷却后在单口烧瓶中加入0.095g苯酚、0.06g多聚甲醛和0.36g甲苯，将分水器更换为冷凝管，升温至90℃回流6h，反应结束后得到固含量为30％的黄色透明液体，从而得到苯并噁嗪树脂。
对比例一
本实施例提供了一种柔性聚酰亚胺溶液的制备方法，具体步骤为：在氮气保护下，在装有磁力搅拌和分水器的单口烧瓶中装入4.01g4，4-二氨基二苯醚和33.77gN-甲基吡咯烷酮，溶解完毕后缓慢加入10.46g双酚A型二醚二酐(BPADA)，在常温下反应1h，升温至140℃反应10h，得到固含量为30％的柔性聚酰亚胺齐聚物溶液。
其中，实施例四至实施例七与对比例一的成分对比情况如下表一：
表一、实施例四至实施例七与对比例一的成分对比表
  实施例四 实施例五 实施例六 实施例七 对比例一
D400 8.40g 6.80g / / /
D230 / / 4.83g / /
ODA / 0.80g / / 4.01g
1074 / / / 11.50g /
BPADA 10.46g 10.46g 10.46g 10.46g 10.46g
苯酚 0.095g 0.095g 0.095g 0.095g /
多聚甲醛 0.06g 0.06g 0.06g 0.06g /
N-甲基吡咯烷酮 44.01g 42.15 35.68 51.25 33.77g
甲苯 0.36g 0.36g 0.36g 0.36g 0.36g
实施例八
本实施例提供了一种胶粘片的制备方法，具体步骤为：将实施例四至实施例七以及对比例一制备得到的组合物，分别将胶粘剂溶液涂布在经过电晕的PI基板上，分别与铜箔进行压合固化制备成为覆铜箔单面板，将有胶粘剂的一侧相对进行压合、固化，制备多层基板。并根据获得的覆铜箔单面板进行相应的性能测试，具体测试如下：
1、剥离强度的测试
按照IPC-TM-650-2.4.8测试规范，将样品裁成3.18mm的样条，启动实验机，以50mm/min的速度在垂直方向上施加拉力，直至最少剥离25.4mm长，测试4次，计算平均值所用设备为电子式万能试验机。
2、耐锡焊性能测试
按照IPC-TM-650-2.4.13测试规范将上述覆铜箔单面板裁成50mm×50m的样条，进行耐锡焊性能测试。
3、介电性能测试
将实施例四-实施例七和比较例一以固化后膜厚50u的方式涂布到PTFE上，在220℃干燥固化20min后剥离，得到膜厚约50um的介电测定用样品按照IPC-TM-650-2.5.5.10测试规范，使用市售的介电常数测试装置(空腔共振器型、AET制造)测试10GHz下的介电常数和介电损耗角正切。
4、DMA测试
设备为TA公司DMA850，测试时使用拉伸模式。
根据上述的剥离强度的测试、耐锡焊性能测试、介电性能测试和DMA测试，其中，基于实施例四至实施例七制备得到的覆铜箔层压板分别作为 实施例四-1、实施例五-1、实施例六-1、实施例七-1，而基于对比例一制备得到的覆铜箔层压板则作为对比例一-1。
实施例四-1至实施例七-1以及对比例一-1的各性能测试结果如下表二所示：
表二、实施例四-1至实施例七-1以及对比例一-1的各性能测试结果表
Figure PCTCN2022121715-appb-000005
其中，图1为实施例四所制样品的红外吸收光谱，图1中可以观察到1775cm-1，1718cm-1,1370cm-1处出现酰亚胺吸收峰，920cm-1处出现微小的噁嗪环特征吸收峰，表明合成了含有酰亚胺结构的苯并噁嗪。
图2为实施例四与比较例一DMA储能模量随温度变化的比较，从图2中可以明显看出本发明提供的具有低介电损耗的覆铜板用粘接剂相较于普通粘接剂具有更好的耐热性。
通过对比可知，实施例四-1至实施例七-1的粘接性能和耐锡焊性能均优于对比例一-1，即说明本发明实施例所提供的低介电损耗的覆铜板用粘接剂具有更优异的粘接性能和更低的介电常数和损耗。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (20)

  1. 一种苯并噁嗪树脂，其特征在于，所述苯并噁嗪树脂的分子式如下：
    Figure PCTCN2022121715-appb-100001
    其中，R 1、R 2、R 3、R 4分别独立的选自-H和烷基、烷氧基、环烷基和芳香基，且其中至少一个基团为-H；X 1为主链或侧链含有长链结构的烷基或/和烷氧基；X 2为单键的烷基、醚基、烷氧基、烷基酯基、羰基、砜基以及硫醚基中的一种或多种，酰亚胺基团重复单元的数目n在1-150之间。
  2. 如权利要求1所述的苯并噁嗪树脂，其特征在于：所述酰亚胺基团重复单元的数目n在20-100之间。
  3. 如权利要求1所述的苯并噁嗪树脂，其特征在于：所述烷基和所述烷氧基中碳原子数为5-30之间。
  4. 一种如权利要求1-3任一项所述的苯并噁嗪树脂的制备方法，其特征在于，所述制备方法包括以下步骤：
    以伯胺封端的柔性聚酰亚胺齐聚物、醛类化合物和单官能酚类化合物为反应物，合成主链含有酰亚胺结构的苯并噁嗪树脂。
  5. 如权利要求4所述的苯并噁嗪树脂的制备方法，其特征在于：所述伯胺封端的柔性聚酰亚胺齐聚物为四羧酸二酐与二元伯胺的产物，所述二元伯胺为主链或侧链含有柔性长链的二胺或其与其他芳香族二胺的混合物。
  6. 如权利要求4所述的苯并噁嗪树脂的制备方法，其特征在于：所述醛类化合物为甲醛和/或多聚甲醛。
  7. 如权利要求4所述的苯并噁嗪树脂的制备方法，其特征在于：所述单官能酚类化合物具有如下结构的分子式：
    Figure PCTCN2022121715-appb-100002
    其中，R 5、R 6、R 7、R 8分别独立的选自-H、烷基、烷氧基、环烷基和芳香基，且其中一个或多个的基团为-H。
  8. 如权利要求7所述的苯并噁嗪树脂的制备方法，其特征在于：所述烷基和所述环烷基中碳原子数为1-10之间。
  9. 如权利要求4所述的苯并噁嗪树脂的制备方法，其特征在于：所述反应物的摩尔比为：
    伯胺封端的柔性聚酰亚胺齐聚物：醛类化合物：单官能酚类化合物＝(0.8-1.2)：(1.6-2.5)：(0.9-1.3)。
  10. 如权利要求5所述的苯并噁嗪树脂的制备方法，其特征在于：所述制备方法还包括：加入溶剂，所述溶剂为甲苯、二甲苯、二氧六环、四氢呋喃、甲醇、乙醇、丙酮、丁酮、环己酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和N-甲基吡咯烷酮中的一种或多种的混合物。
  11. 如权利要求4所述的苯并噁嗪树脂的制备方法，其特征在于：所述反应物在反应过程中，反应温度为60℃-180℃，反应时间为0.5h-10h。
  12. 如权利要求10所述的苯并噁嗪树脂的制备方法，其特征在于：所述伯胺封端的柔性聚酰亚胺齐聚物的制备方法包括以下步骤：
    S1、在氮气的保护的条件下，将所述二元伯胺溶解在所述溶剂中形成第一混合溶剂；
    S2、往所述第一混合溶剂中逐步加入所述四羧酸二酐；
    S3、通过在第一预设温度的条件下，持续反应第一预设时间以得到第二混合溶剂；
    S4、往所述第二混合溶剂中加入催化剂或带水剂，并使其在第二预设 温度的条件下，亚胺化处理第二预设时间，之后析出或干燥后得到所述伯胺封端的柔性聚酰亚胺齐聚物。
  13. 如权利要求12所述的苯并噁嗪树脂的制备方法，其特征在于：所述四羧酸二酐成分与所述二元伯胺成分的摩尔数的比率为1≤(二元伯胺/四羧酸二酐)＜1.1。
  14. 如权利要求12所述的苯并噁嗪树脂的制备方法，其特征在于：所述第一预设温度为-20℃-30℃，所述第一预设时间为0.5h-24h。
  15. 如权利要求5所述的苯并噁嗪树脂的制备方法，其特征在于：所述四羧酸二酐为3,3’,4,4’联苯四羧酸二酐、4,4’联苯醚二酐、3,3’,4,4’二苯酮四酸二酐、六氟二酐、双酚A型二醚二酐和均苯四甲酸酐中的一种或多种。
  16. 如权利要求5所述的苯并噁嗪树脂的制备方法，其特征在于：所述主链或侧链含有柔性长链的二胺的分子式如下：
    H 2N——X 3——NH 2；
    其中，X 3为主链或侧链含有长链结构的烷基或/和烷氧基；
    所述芳香族二胺为间苯二胺、4，4-二氨基二苯醚、对苯二胺、1，3-双(3-氨基苯氧基)苯、1，3-双(4-氨基苯氧基)苯和1，4-双(4-氨基苯氧基)苯中的一种或多种。
  17. 如权利要求16所述的苯并噁嗪树脂的制备方法，其特征在于：所述主链或侧链含有柔性长链的二胺与芳香族二胺摩尔比为2:8-10:0。
  18. 如权利要求4所述的苯并噁嗪树脂的制备方法，其特征在于：所述伯胺封端的柔性聚酰亚胺齐聚物的分子量为Mn1000-100000。
  19. 一种胶粘剂，其特征在于：所述胶粘剂包括权利要求4至18任意一项所述苯并噁嗪树脂的制备方法制得的苯并噁嗪树脂。
  20. 如权利要求19所述的胶粘剂，其特征在于：所述胶粘剂应用于膜状胶粘材料、胶粘层、胶粘片、带树脂的铜箔、覆铜箔层压板以及树脂多层基板。
PCT/CN2022/121715 2022-09-05 2022-09-27 苯并噁嗪树脂、制备方法及胶粘剂 WO2024050891A1 (zh)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015130464A1 (en) * 2014-02-26 2015-09-03 Huntsman Advanced Materials Americas Llc Reaction hybrid benzoxazine resins and uses thereof
CN108148077A (zh) * 2018-01-24 2018-06-12 长沙新材料产业研究院有限公司 一种含酰亚胺基的苯并噁嗪树脂中间体及其制备方法
CN110655650A (zh) * 2019-11-11 2020-01-07 同济大学 一种苯并噁嗪桥连型聚酰亚胺前驱体及其制备方法
CN110804409A (zh) * 2019-12-03 2020-02-18 山东大学 一种聚酰亚胺用苯并噁嗪型胶粘剂及其制备与使用方法
JP2022053324A (ja) * 2020-09-24 2022-04-05 株式会社カネカ ベンゾオキサジン系熱硬化性樹脂、およびその製造方法
CN114805802A (zh) * 2022-04-01 2022-07-29 华南理工大学 苯并噁嗪封端型酰亚胺及其制备方法和聚苯并噁嗪封端型酰亚胺膜
CN114957156A (zh) * 2022-05-25 2022-08-30 成都科宜高分子科技有限公司 一种含苯并噁嗪结构的化合物、树脂组合物、半固化片、电覆铜板及其制备方法、应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110042831A (ko) * 2009-10-20 2011-04-27 주식회사 두산 폴리아믹산 용액, 폴리이미드 수지 및 이를 이용한 연성 동박 적층판
CN110818868B (zh) * 2019-11-29 2023-12-12 淮北绿洲新材料有限责任公司 一元胺封端的超高频低介电性主链苯并噁嗪共聚物低聚体、共聚树脂及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015130464A1 (en) * 2014-02-26 2015-09-03 Huntsman Advanced Materials Americas Llc Reaction hybrid benzoxazine resins and uses thereof
CN108148077A (zh) * 2018-01-24 2018-06-12 长沙新材料产业研究院有限公司 一种含酰亚胺基的苯并噁嗪树脂中间体及其制备方法
CN110655650A (zh) * 2019-11-11 2020-01-07 同济大学 一种苯并噁嗪桥连型聚酰亚胺前驱体及其制备方法
CN110804409A (zh) * 2019-12-03 2020-02-18 山东大学 一种聚酰亚胺用苯并噁嗪型胶粘剂及其制备与使用方法
JP2022053324A (ja) * 2020-09-24 2022-04-05 株式会社カネカ ベンゾオキサジン系熱硬化性樹脂、およびその製造方法
CN114805802A (zh) * 2022-04-01 2022-07-29 华南理工大学 苯并噁嗪封端型酰亚胺及其制备方法和聚苯并噁嗪封端型酰亚胺膜
CN114957156A (zh) * 2022-05-25 2022-08-30 成都科宜高分子科技有限公司 一种含苯并噁嗪结构的化合物、树脂组合物、半固化片、电覆铜板及其制备方法、应用

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