CN110655791B - High heat-resistant low-dielectric active ester resin composition and preparation method of laminated board - Google Patents

High heat-resistant low-dielectric active ester resin composition and preparation method of laminated board Download PDF

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CN110655791B
CN110655791B CN201910941263.5A CN201910941263A CN110655791B CN 110655791 B CN110655791 B CN 110655791B CN 201910941263 A CN201910941263 A CN 201910941263A CN 110655791 B CN110655791 B CN 110655791B
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resin
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maleimide
phenol
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CN110655791A (en
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邹静
周友
陈立兴
伍驰旻
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Aimont Chengdu New Material Technology Co ltd
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B15/00—Layered products comprising a layer of metal
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    • B32—LAYERED PRODUCTS
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    • B32B2260/04—Impregnation, embedding, or binder material
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • 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
    • B32B2307/7265—Non-permeable
    • 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
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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    • 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

Abstract

The invention discloses a preparation method of a high-heat-resistance low-dielectric activity ester resin composition and a laminated board, which is characterized by comprising the following steps: the high heat-resistant low-dielectric active ester resin composition is prepared by mixing 100 parts by mass of active ester maleimide resin, 40-80 parts by mass of epoxy resin, 0.2-0.6 part by mass of accelerator, 10-25 parts by mass of bismaleimide diphenyl methyl ether or bismaleimide diphenylmethane and 45-76 parts by mass of filler; soaking glass fiber cloth in the composition, and heating and drying at 150-170 ℃ for 1-4 min to obtain a prepreg; laminating 3-16 prepregs, attaching copper foils on two surfaces of the prepregs, placing the prepregs in a hot press at 160-170 ℃, pressurizing to 0.2-4 MPa, pressing for 0.5-1 h, heating to 180-250 ℃, hot-pressing for 3-5 h, and naturally cooling to obtain the high-heat-resistance low-dielectric-constant active ester resin laminated board which can be widely applied to the field of printed circuit boards and has good performance.

Description

High heat-resistant low-dielectric active ester resin composition and preparation method of laminated board
Technical Field
The invention belongs to preparation of a composition and a laminated board, and particularly relates to a high-heat-resistance low-dielectric activity ester resin composition and a preparation method of the laminated board. The high heat-resistant low-dielectric active ester resin composition can be widely applied to the technical field of electronics such as printed circuit boards.
Background
In recent years, with the rapid development of information industry, electronic products are becoming shorter, thinner, higher in performance and multifunctional, and in order to meet the development requirements of various electronic devices, information communication devices tend to be higher in signal transmission speed and higher in frequency, and integrated circuits are advancing to the direction of higher density, higher precision and higher integration, which requires that printed circuit board substrate materials have good dielectric properties (i.e., low dielectric constant and dielectric loss) and also require that substrates have good heat resistance to meet the process reliability requirements of the printed circuit boards. The bismaleimide resin is a high-performance matrix resin, has excellent dielectric property, heat resistance, mechanical property and the like, and has a prominent application prospect in the field of printed circuit boards. However, bismaleimide resins are brittle and are often used in combination with diallyl bisphenol a and epoxy resins in laminate applications, and the resulting cured resin contains polar secondary hydroxyl groups, so that the laminate has high dielectric properties. The related literature reports that the dielectric constant of the epoxy resin and diallyl bisphenol A toughened bismaleimide laminated board is about 4.1-4.7 at 1GHz, and the dielectric loss is 0.09-0.12. In the prior art, the influence of secondary hydroxyl of an epoxy resin condensate on the dielectric property of a laminated board can be solved by adopting an active ester curing agent. CN 106893258A discloses an epoxy resin composition, and a prepreg, a laminated board and a printed circuit board containing the same, wherein the laminated board prepared from the epoxy resin and polyester type active ester containing a rigid structure has low dielectric loss (0.007-0.0102) and glass transition temperature Tg (153-168 ℃) at high frequency (10GHz), and although the laminated board has excellent dielectric properties, the heat resistance is difficult to meet the development requirement of the current printed circuit board.
Disclosure of Invention
The present invention aims to overcome the defects in the prior art and provide a preparation method of a high heat-resistant low-dielectric active ester resin composition and a laminated board. The high-heat-resistance low-dielectric active ester resin composition provided by the invention contains active ester type maleimide resin, integrates the advantages of active ester and bismaleimide resin, can better solve the technical problem of poor dielectric property of the existing epoxy resin and diallyl bisphenol A toughened bismaleimide resin-based laminated board, and the prepared laminated board has good heat resistance, dielectric property and moisture absorption property, wherein the glass transition temperature Tg is 241-257 ℃, the water absorption rate is 0.15-0.25%, the dielectric constant Dk is 3.49-3.75 at 10GHz, and the dielectric loss Df is 0.005-0.007.
The content of the invention is as follows: a high heat-resistant low-dielectric active ester resin composition is characterized in that: the high heat-resistant low-dielectric active ester resin composition is formed by mixing 100 parts by mass of active ester maleimide resin, 40-80 parts by mass of epoxy resin, 0.2-0.6 part by mass of accelerator, 10-25 parts by mass of bismaleimide diphenyl methyl ether (OBMI) or Bismaleimide Diphenylmethane (BDM) and 45-76 parts by mass of filler;
the active ester type maleimide resin is a maleimide resin containing two or more active ester group structures; the active ester type maleimide resin may be any one of polyester type maleimide resin (self-made), dicyclopentadiene phenol ester type maleimide resin (self-made), novolak type maleimide resin (for example, phenol novolak type maleimide resin, orthocresol novolak ester type maleimide resin, phenol aralkyl novolak type maleimide resin, bisphenol A novolak type maleimide resin, etc.) (self-made);
the epoxy resin is an aromatic compound containing two or more epoxy groups, and can be any one of bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin (phenol formaldehyde novolac type epoxy resin, o-cresol formaldehyde novolac type epoxy resin, bisphenol A formaldehyde novolac type epoxy resin) and dicyclopentadiene phenol type epoxy resin; the production and supply enterprises of epoxy resin products are as follows: jinan Shengquan group, Inc., Jiannshengde materials science and technology, Inc., Wuxi Lanxing petrochemical, Inc., Nanya New materials science and technology, Inc., Shenzhen Jia Dida New materials science and technology, Inc., etc.;
the accelerant is any one of 2,4, 6-tri (dimethylaminomethyl) phenol (DMP-30 for short), triphenylphosphine (TPP for short), 4-dimethylaminopyridine, 2-methylimidazole, 1-benzyl-2-methylimidazole and the like;
the filler is any one of silicon dioxide, montmorillonite, magnesium oxide, aluminum oxide, mica powder and the like.
The invention comprises the following steps: the polyester maleimide resin is a compound having a general chemical structure represented by formula (1):
Figure BDA0002222970570000021
in formula (1): m is 2 to 4, Ar1And Ar2The aromatic group can be phenyl, naphthyl, biphenyl and the groups which are substituted by C1-C3 alkyl, alkoxy, halogen and the like; the R group is phenyl or alkyl group with 2-5 carbon atoms;
the dicyclopentadiene phenol ester type maleimide resin is a compound having a general chemical structure represented by formula (2):
Figure BDA0002222970570000031
in formula (2): n is 1 to 3, and X is
Figure BDA0002222970570000032
The novolak type maleimide resin is a compound having a general chemical structure represented by the formula (3-1, 3-2 or 3-3):
Figure BDA0002222970570000033
a phenol novolac maleimide resin and a mono-substituted phenol novolac maleimide resin of formula (3-1) (e.g., an o-cresol novolac maleimide resin and an m-cresol novolac maleimide resin), wherein in formula (3-1), k is 1 to 3, and X is
Figure BDA0002222970570000034
Y is C1-C3 alkyl, C1-C3 alkoxy, chlorine, bromine, fluorine and the like;
Figure BDA0002222970570000035
a phenol aralkyl novolak type maleimide resin of the formula (3-2) wherein: j is 1 to 3, and X is
Figure BDA0002222970570000041
Figure BDA0002222970570000042
A bisphenol A novolac type maleimide resin of the formula (3-3), wherein: g is 1 to 3, and X is
Figure BDA0002222970570000043
The invention comprises the following steps: the preparation of the polyester maleimide resin is carried out by reacting aromatic dihydric phenol, esterifying agent, end-capping agent and alkaline catalyst in organic solvent; the specific preparation method of the polyester maleimide resin comprises the following steps: dissolving 0.4mol of aromatic dihydric phenol and 0.24mol to 0.32mol of esterifying agent in 650 to 950 parts by mass of organic solvent, reacting for 2 to 3 hours at the temperature of 50 to 80 ℃ under the action of 0.22 to 0.68mol of alkaline catalyst, then adding 0.23 to 0.38mol of end capping agent, continuing to react for 2 to 3 hours, filtering and washing to be neutral after the reaction is finished, and removing the organic solvent through reduced pressure distillation to prepare the polyester maleimide resin;
the aromatic dihydric phenol is one or a mixture of two of aromatic phenol compounds such as catechol, resorcinol, hydroquinone, 1, 4-naphthalenediol, 2, 6-naphthalenediol, 2 '-biphenyldiol and 4,4' -biphenyldiol, and aromatic phenol compounds obtained by substituting the aromatic phenol compounds (namely the aromatic phenol compounds) with C1-C3 alkyl, alkoxy, halogen and the like;
the esterifying agent is aromatic dibasic acid or anhydride such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic anhydride, 4-chloro-1, 8-naphthalenedicarboxylic anhydride, 2' -biphenyldicarboxylic acid, 4' -biphenyldicarboxylic acid, 2' -biphenyldicarboxylic anhydride, etc., and aromatic acid chloride compounds such as phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, 1, 4-naphthalenedicarboxylic acid chloride, 2, 6-naphthalenedicarboxylic acid chloride, 2 '-biphenyldicarbonyl chloride, 4' -biphenyldicarbonyl chloride, and one or a mixture of two of the above aromatic compounds which are mono-substituted with a C1-C3 alkyl group, an alkoxy group, a halogen or the like;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide (DMF for short), dimethylacetamide (DMAc for short) and N-methylpyrrolidone (NMP for short).
The invention comprises the following steps: the dicyclopentadiene phenol ester type maleimide resin is prepared by reacting dicyclopentadiene phenol, a blocking agent and an alkaline catalyst in an organic solvent; the specific preparation method of the dicyclopentadiene phenol ester type maleimide resin comprises the following steps: dissolving 100 parts by mass of dicyclopentadiene phenol and 164-308 parts by mass of an end-capping reagent in 500-1000 parts by mass of an organic solvent, reacting at 50-80 ℃ for 2-3 h under the action of 17-116 parts by mass of an alkaline catalyst, filtering, washing to neutrality, and distilling under reduced pressure to remove the organic solvent to obtain dicyclopentadiene phenol ester type maleimide resin;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide (DMF for short), dimethylacetamide (DMAc for short) and N-methylpyrrolidone (NMP for short).
The invention comprises the following steps: the novolac-type maleimide resin (such as phenol novolac-type maleimide resin, o-cresol novolac-type maleimide resin, phenol aralkyl novolac-type maleimide resin, bisphenol A novolac-type maleimide resin and the like) is prepared by reacting novolac resin, a blocking agent and an alkaline catalyst in an organic solvent; the specific preparation method of the novolac phenolic ester maleimide resin comprises the following steps: dissolving 100 parts by mass of phenolic novolac resin and 164-308 parts by mass of end-capping reagent in 500-1000 parts by mass of organic solvent, reacting for 2-3 h at 50-80 ℃ under the action of 17-116 parts by mass of alkaline catalyst, filtering, washing to neutrality with water, and distilling under reduced pressure to remove the organic solvent to obtain phenolic novolac ester type maleimide resin;
the linear phenolic resin is any one of phenol type phenolic resin, o-cresol phenolic resin, m-cresol phenolic resin, bisphenol A formaldehyde resin and phenol aralkyl phenolic resin;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide (DMF for short), dimethylacetamide (DMAc for short) and N-methylpyrrolidone (NMP for short).
Another aspect of the invention is: a preparation method of a high-heat-resistance low-dielectric-activity ester resin laminated board is characterized by comprising the following steps: uniformly dispersing a high-heat-resistance low-dielectric resin composition containing 100 parts by mass of active ester type maleimide resin, 40-80 parts by mass of epoxy resin, 0.2-0.6 part by mass of an accelerator, 10-25 parts by mass of bismaleimide diphenyl methyl ether (OBMI) or Bismaleimide Diphenylmethane (BDM) and 45-76 parts by mass of a filler in a proper amount of an organic solvent to prepare a prepreg with the solid content of 60-70%, taking glass fiber cloth to soak in the prepreg, taking out the prepreg, and heating and drying the prepreg for 1-4 min at the temperature of 150-170 ℃ to obtain the prepreg; laminating 3-16 layers of prepregs, attaching copper foils on two surfaces of the prepregs, placing the prepregs in a hot press at 160-170 ℃, pressurizing to 0.2-4 MPa (according to the condition of flow adhesives), laminating for 0.5-1 h, gradually heating to 180-250 ℃, hot-pressing for 3-5 h, and naturally cooling to obtain the high-heat-resistance low-dielectric-constant active ester resin laminated board;
the definition of the prepreg with the solid content of 60-70% is as follows: 100g of the prepreg was baked in an oven at 125 ℃ for 3 hours, and the mass of the non-volatile matter was calculated as a percentage of the total mass, and the amount of solid finally determined by the mass blending of the added solvent was calculated based on the mass of the non-volatile matter.
The active ester type maleimide resin is a maleimide resin containing two or more active ester group structures; the active ester type maleimide resin may be any one of polyester type maleimide resin (self-made), dicyclopentadiene phenol ester type maleimide resin (self-made), novolak type maleimide resin (for example, phenol novolak type maleimide resin, o-cresol novolak ester type maleimide resin, phenol aralkyl novolak type maleimide resin, bisphenol A novolak type maleimide resin, etc.) (self-made);
the epoxy resin is an aromatic compound containing two or more epoxy groups, and can be any one of bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin (phenol formaldehyde novolac type epoxy resin, o-cresol formaldehyde novolac type epoxy resin, bisphenol A formaldehyde novolac type epoxy resin) and dicyclopentadiene phenol type epoxy resin; the production and supply enterprises of epoxy resin products are as follows: jinan Shengquan group, Inc., Jiannshengde materials science and technology, Inc., Wuxi Lanxing petrochemical, Inc., Nanya New materials science and technology, Inc., Shenzhen Jia Dida New materials science and technology, Inc., etc.;
the accelerant is any one of 2,4, 6-tri (dimethylaminomethyl) phenol (DMP-30 for short), triphenylphosphine (TPP for short), 4-dimethylaminopyridine, 2-methylimidazole, 1-benzyl-2-methylimidazole and the like;
the filler is any one of silicon dioxide, montmorillonite, magnesium oxide, aluminum oxide, mica powder and the like;
the organic solvent is any one of acetone, butanone, methyl isobutyl ketone, propylene glycol monomethyl ether and ethylene glycol methyl ether.
The prepared high-heat-resistance low-dielectric-activity ester resin laminated board has excellent comprehensive performance, and the related technical performance parameters are as follows: a glass transition temperature Tg of 241-257 ℃, a water absorption of 0.15-0.25%, a dielectric constant Dk of 3.49-3.75 at 10GHz, and a dielectric loss Df of 0.005-0.007.
In another aspect of the invention: the polyester maleimide resin is a compound having a general chemical structure represented by formula (1):
Figure BDA0002222970570000071
in formula (1): m is 2 to 4, Ar1And Ar2The aromatic group can be phenyl, naphthyl, biphenyl and the groups which are substituted by C1-C3 alkyl, alkoxy, halogen and the like; the R group is phenyl or alkyl group with 2-5 carbon atoms;
the dicyclopentadiene phenol ester type maleimide resin is a compound having a general chemical structure represented by formula (2):
Figure BDA0002222970570000072
in formula (2): n is 1 to 3, and X is
Figure BDA0002222970570000073
The novolak type maleimide resin is a compound having a general chemical structure represented by the formula (3-1, 3-2 or 3-3):
Figure BDA0002222970570000081
a phenol novolac maleimide resin and a mono-substituted phenol novolac maleimide resin of formula (3-1) (e.g., an o-cresol novolac maleimide resin and an m-cresol novolac maleimide resin), wherein in formula (3-1), k is 1 to 3, and X is
Figure BDA0002222970570000082
Y is C1-C3 alkyl, C1-C3 alkoxy, chlorine, bromine, fluorine and the like;
Figure BDA0002222970570000083
a phenol aralkyl novolak type maleimide resin of the formula (3-2) wherein: j is 1 to 3, and X is
Figure BDA0002222970570000084
Figure BDA0002222970570000085
A bisphenol A novolac type maleimide resin of the formula (3-3), wherein: g is 1 to 3, and X is
Figure BDA0002222970570000086
In another aspect of the invention: the preparation of the polyester maleimide resin is carried out by reacting aromatic dihydric phenol, esterifying agent, end-capping agent and alkaline catalyst in organic solvent; the specific preparation method of the polyester maleimide resin comprises the following steps: dissolving 0.4mol of aromatic dihydric phenol and 0.24mol to 0.32mol of esterifying agent in 650 to 950 parts by mass of organic solvent, reacting for 2 to 3 hours at the temperature of 50 to 80 ℃ under the action of 0.22 to 0.68mol of alkaline catalyst, then adding 0.23 to 0.38mol of end capping agent, continuing to react for 2 to 3 hours, filtering and washing to be neutral after the reaction is finished, and removing the organic solvent through reduced pressure distillation to prepare the polyester maleimide resin;
the aromatic dihydric phenol is one or a mixture of two of aromatic phenol compounds such as catechol, resorcinol, hydroquinone, 1, 4-naphthalenediol, 2, 6-naphthalenediol, 2 '-biphenyldiol and 4,4' -biphenyldiol, and aromatic phenol compounds obtained by substituting the aromatic phenol compounds (namely the aromatic phenol compounds) with C1-C3 alkyl, alkoxy, halogen and the like;
the esterifying agent is aromatic dibasic acid or anhydride such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic anhydride, 4-chloro-1, 8-naphthalenedicarboxylic anhydride, 2' -biphenyldicarboxylic acid, 4' -biphenyldicarboxylic acid, 2' -biphenyldicarboxylic anhydride, etc., and aromatic acid chloride compounds such as phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, 1, 4-naphthalenedicarboxylic acid chloride, 2, 6-naphthalenedicarboxylic acid chloride, 2 '-biphenyldicarbonyl chloride, 4' -biphenyldicarbonyl chloride, and one or a mixture of two of the above aromatic compounds which are mono-substituted with a C1-C3 alkyl group, an alkoxy group, a halogen or the like;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide (DMF for short), dimethylacetamide (DMAc for short) and N-methylpyrrolidone (NMP for short).
In another aspect of the invention: the dicyclopentadiene phenol ester type maleimide resin is prepared by reacting dicyclopentadiene phenol, a blocking agent and an alkaline catalyst in an organic solvent; the specific preparation method of the dicyclopentadiene phenol ester type maleimide resin comprises the following steps: dissolving 100 parts by mass of dicyclopentadiene phenol and 164-308 parts by mass of an end-capping reagent in 500-1000 parts by mass of an organic solvent, reacting at 50-80 ℃ for 2-3 h under the action of 17-116 parts by mass of an alkaline catalyst, filtering, washing to neutrality, and distilling under reduced pressure to remove the organic solvent to obtain dicyclopentadiene phenol ester type maleimide resin;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide (DMF for short), dimethylacetamide (DMAc for short) and N-methylpyrrolidone (NMP for short).
In another aspect of the invention: the novolac-type maleimide resin (such as phenol novolac-type maleimide resin, o-cresol novolac-type maleimide resin, phenol aralkyl novolac-type maleimide resin, bisphenol A novolac-type maleimide resin and the like) is prepared by reacting novolac resin, a blocking agent and an alkaline catalyst in an organic solvent; the specific preparation method of the novolac phenolic ester maleimide resin comprises the following steps: dissolving 100 parts by mass of phenolic novolac resin and 164-308 parts by mass of end-capping reagent in 500-1000 parts by mass of organic solvent, reacting for 2-3 h at 50-80 ℃ under the action of 17-116 parts by mass of alkaline catalyst, filtering, washing to neutrality with water, and distilling under reduced pressure to remove the organic solvent to obtain phenolic novolac ester type maleimide resin;
the linear phenolic resin is any one of phenol type phenolic resin, o-cresol phenolic resin, m-cresol phenolic resin, bisphenol A formaldehyde resin and phenol aralkyl phenolic resin; the product providing enterprises have: the Jinan Shengquan group, the Jiannan Jiasheng materials science and technology, the Sichuan east materials science and technology group, and the like;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide (DMF for short), dimethylacetamide (DMAc for short) and N-methylpyrrolidone (NMP for short).
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) compared with epoxy resin and diallyl bisphenol A toughened bismaleimide resin systems, the active ester maleimide resin has the function of an epoxy curing agent when the epoxy resin is used as a toughening modifier, can directly react with the epoxy resin without adding a curing agent (such as diallyl bisphenol A), and simultaneously has maleimide crosslinking reaction, so that polar secondary hydroxyl is not generated in the reaction process, and a cured resin is endowed with good dielectric property and heat resistance;
(2) the high heat-resistant low-dielectric resin composition provided by the invention comprises the active ester curing agent containing the maleimide structure, the cured resin composition avoids the adverse effect of secondary hydroxyl on the performance of a laminated board on the basis of keeping the performance characteristics of the bismaleimide resin, and the prepared laminated board has good comprehensive performance: the glass transition temperature Tg is 241-257 ℃, the water absorption is 0.15-0.25%, the dielectric constant Dk is 3.49-3.75 at 10GHz, and the dielectric loss Df is 0.005-0.007;
(3) the product of the invention has simple preparation process, easy operation and strong practicability.
Detailed Description
The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.
Preparation of the first part active ester type Maleimide resin
1. Embodiments of the polyester maleimide resin:
(1) dissolving 0.4mol of aromatic dihydric phenol and 0.24mol to 0.32mol of esterifying agent in 650 to 950 mass parts of organic solvent, and reacting for 2 to 3 hours at 50 to 80 ℃ under the action of 0.22 to 0.68mol of alkaline catalyst;
(2) adding 0.23-0.38 mol of end-capping reagent, continuing to react for 2-3 h, filtering, washing with water to neutrality after the reaction is finished, and removing the organic solvent to obtain the active ester type maleimide resin of the embodiment 1-5.
The material components and amounts in the examples are given in table 1 below:
table 1: compounding list and index parameter list of polyester type maleimide resin
Figure BDA0002222970570000111
Figure BDA0002222970570000121
2. Embodiments of the dicyclopentadiene phenol ester type maleimide resin, the novolak type maleimide resin: dissolving 100 parts by mass of a phenol compound (dicyclopentadiene phenol or novolac resin) and 164-308 parts by mass of a blocking agent in 500-1000 parts by mass of an organic solvent, reacting at 50-80 ℃ for 2-3 hours under the action of 17-116 parts by mass of an alkaline catalyst, filtering, washing with water to neutrality, and removing the organic solvent to obtain the active ester type maleimide resin of examples 2-1-2-5.
Table 2: dicyclopentadiene phenol ester type maleimide resin, novolac phenol ester type maleimide resin batching table and index parameter table
Figure BDA0002222970570000122
Figure BDA0002222970570000131
Table 2 notes: phenol type phenol resin: PF-8010 of Shengquan, and the hydroxyl equivalent is 105-109 g/eq; o-cresol novolac resin: shengquan SH-3080, the hydroxyl equivalent weight is 117-122 g/eq; bisphenol a formaldehyde resin: shengquan SH-2113, the hydroxyl equivalent is 110-116 g/eq; phenol aralkyl phenol resin: shengquan SH-4064, the hydroxyl equivalent is 168-174 g/eq; dicyclopentadiene phenol: shengquan SH-7090, the hydroxyl equivalent weight is 180-190 g/eq; the unit of the amount of the components "part" in the table means part by mass.
Preparation of second part high heat-resistant low dielectric laminated board
1. Embodiments of the high heat resistant low dielectric laminate:
(1) uniformly dispersing the high-heat-resistance low-dielectric resin composition in an organic solvent to prepare a prepreg with a solid content of 65%, impregnating the prepreg with glass fiber cloth, and heating and drying the prepreg at 150-170 ℃ for 1-4 min to obtain a prepreg;
(2) laminating 3-16 layers of prepregs, attaching copper foils on two surfaces of the prepregs, placing the prepregs in a hot press at 160-170 ℃, gradually pressurizing to 0.2-4 MPa according to the condition of the flow adhesive, laminating for 0.5-1 h, gradually heating to 180-250 ℃, and hot-pressing for 3-5 h to obtain the high-heat-resistance low-dielectric laminated board of the embodiment 3-1-3-10.
Wherein: the high heat resistant low dielectric resin composition comprises: 100 parts by mass of active ester type maleimide resin, 40-80 parts by mass of epoxy resin, 0.2-0.6 part by mass of accelerator, 10-25 parts by mass of bismaleimide diphenyl methyl ether (OBMI) or Bismaleimide Diphenylmethane (BDM) and 45-76 parts by mass of filler; the organic solvent is one of acetone, butanone, methyl isobutyl ketone, propylene glycol monomethyl ether and ethylene glycol methyl ether.
Table 3: material proportioning table and performance parameter table of high heat-resistant low dielectric laminate in examples 3-1 to 3-10
Figure BDA0002222970570000132
Figure BDA0002222970570000141
Note: the unit of the use amount of the components in Table 3 is parts by mass; SQCN 703: the epoxy equivalent of the Shengquan O-cresol formaldehyde epoxy resin is 200-210 g/eq; DPNE 1501: the epoxy equivalent of the Jiasheng dicyclopentadiene phenol type epoxy resin is 253-268g/eq
Comparative example 1:
stirring 150 parts by mass of BMI, 100 parts by mass of diallyl bisphenol A and 50 parts by mass of epoxy resin at 140 ℃ for 1h, cooling, adding 35 parts by mass of silicon dioxide and a proper amount of solvent, uniformly mixing to prepare a resin solution with a solid content of 60-70%, and then soaking the resin solution with glass fiber cloth to prepare the laminated board of the comparative example 1 according to the preparation method of the laminated board of the examples 2-1-2-10.
Comparative example 2:
48 parts by mass of epoxy resin SQCN703, 52 parts by mass of active ester curing agent HPC8000-65T (ester equivalent 223g/eq), 0.3 part by mass of DMP-30, 35 parts by mass of silicon dioxide and a proper amount of solvent are uniformly stirred and mixed to prepare 60-70% resin glue solution, the laminated board of the comparative example is prepared according to the preparation method of the laminated board of the examples 2-1 to 2-10, and the prepared laminated board has the Tg 165 ℃, the water absorption rate of 0.45%, the Dk 3.86 at 10GHz and the Df 0.007.
Example 4:
the high heat-resistant low-dielectric active ester resin composition is formed by mixing 100 parts by mass of active ester type maleimide resin, 40 parts by mass of epoxy resin, 0.2 part by mass of accelerator, 10 parts by mass of bismaleimide diphenyl methyl ether (OBMI) or Bismaleimide Diphenylmethane (BDM) and 45 parts by mass of filler.
Example 5:
the high heat-resistant low-dielectric active ester resin composition is formed by mixing 100 parts by mass of active ester type maleimide resin, 80 parts by mass of epoxy resin, 0.6 part by mass of accelerator, 25 parts by mass of bismaleimide diphenyl methyl ether (OBMI) or Bismaleimide Diphenylmethane (BDM) and 76 parts by mass of filler.
Example 6:
the high heat-resistant low-dielectric active ester resin composition is formed by mixing 100 parts by mass of active ester type maleimide resin, 60 parts by mass of epoxy resin, 0.5 part by mass of accelerator, 17.5 parts by mass of bismaleimide diphenyl methyl ether (OBMI) or Bismaleimide Diphenylmethane (BDM) and 61 parts by mass of filler.
Example 7:
the high heat-resistant low-dielectric active ester resin composition is formed by mixing 100 parts by mass of active ester type maleimide resin, 40-80 parts by mass of any one of epoxy resin, 0.2-0.6 part by mass of any one of accelerant, 10-25 parts by mass of bismaleimide diphenyl methyl ether (OBMI) or Bismaleimide Diphenylmethane (BDM) and 45-76 parts by mass of any one of filler.
Example 8:
a preparation method of a high-heat-resistance low-dielectric-activity ester resin laminated board comprises the following steps: uniformly dispersing a high-heat-resistance low-dielectric resin composition containing 100 parts by mass of active ester type maleimide resin, 40 parts by mass of epoxy resin, 0.2 part by mass of an accelerator, 10 parts by mass of bismaleimide diphenyl methyl ether (OBMI) or Bismaleimide Diphenylmethane (BDM) and 45 parts by mass of a filler in an appropriate amount of an organic solvent to prepare a prepreg with the solid content of 60%, soaking glass fiber cloth in the prepreg, taking out the prepreg, and heating and drying the prepreg for 4min at the temperature of 150 ℃ to obtain the prepreg; laminating 3 layers of prepregs, attaching copper foils on two sides, placing the prepregs in a hot press, placing the prepregs in the hot press at 160 ℃, pressurizing to 0.2MPa (according to the condition of the flow adhesive, gradually) and laminating for 0.5h, gradually heating to 180 ℃ for hot pressing for 5h, and naturally cooling to obtain the high-heat-resistance low-dielectric active ester resin laminated board.
The definition of the prepreg with the solid content of 60% is as follows: 100g of the prepreg was baked in an oven at 125 ℃ for 3 hours, and the mass of the non-volatile matter accounted for 60% of the total mass, and the amount of solid finally determined by mass blending of the added solvent was calculated based on the mass of the non-volatile matter.
Example 9:
a preparation method of a high-heat-resistance low-dielectric-activity ester resin laminated board comprises the following steps: uniformly dispersing a high-heat-resistance low-dielectric resin composition containing 100 parts by mass of active ester type maleimide resin, 80 parts by mass of epoxy resin, 0.6 part by mass of an accelerator, 25 parts by mass of bismaleimide diphenyl methyl ether (OBMI) or Bismaleimide Diphenylmethane (BDM) and 76 parts by mass of a filler in an appropriate amount of an organic solvent to prepare a prepreg with the solid content of 70%, taking out a glass fiber cloth after soaking in the prepreg, and heating and drying at the temperature of 170 ℃ for 1min to obtain the prepreg; laminating 16 prepregs, attaching copper foils on two sides, placing in a hot press, placing in a 170 ℃ hot press, pressurizing to 4MPa (according to the condition of the flow adhesive), laminating for 1h, gradually heating to 250 ℃ for hot pressing for 3h, and naturally cooling to obtain the high-heat-resistance low-dielectric active ester resin laminated board.
The definition of the prepreg with the solid content of 70% is that the mass of non-volatile matters accounts for 70% of the total mass after 100g of the prepreg is baked in an oven at 125 ℃ for 3 hours, and the solid content finally determined by the mass blending of the added solvent is calculated according to the mass of the non-volatile matters.
Example 10:
a preparation method of a high-heat-resistance low-dielectric-activity ester resin laminated board comprises the following steps: uniformly dispersing a high-heat-resistance low-dielectric resin composition containing 100 parts by mass of active ester type maleimide resin, 60 parts by mass of epoxy resin, 0.4 part by mass of an accelerator, 17.5 parts by mass of bismaleimide diphenyl methyl ether (OBMI) or Bismaleimide Diphenylmethane (BDM) and 60.5 parts by mass of a filler in a proper amount of an organic solvent to prepare a prepreg with the solid content of 65%, taking out the glass fiber cloth after dipping in the prepreg, and heating and drying at the temperature of 160 ℃ for 3min to obtain a prepreg; laminating 9 layers of prepregs, attaching copper foils on two sides, placing the prepregs in a hot press, placing the prepregs in the hot press at 165 ℃, pressurizing to 2MPa (according to the condition of the flow adhesive), laminating for 0.8h, gradually heating to 220 ℃, hot-pressing for 4h, and naturally cooling to obtain the high-heat-resistance low-dielectric active ester resin laminated board.
The definition of the prepreg with a solid content of 65% is: 100g of the prepreg was baked in an oven at 125 ℃ for 3 hours, and the mass of the non-volatile matter accounted for 65% of the total mass, and the amount of solid finally determined by mass blending of the added solvent was calculated based on the mass of the non-volatile matter.
Example 11:
a preparation method of a high-heat-resistance low-dielectric-activity ester resin laminated board comprises the following steps: uniformly dispersing a high-heat-resistance low-dielectric resin composition containing 100 parts by mass of active ester type maleimide resin, 50 parts by mass of epoxy resin, 0.3 part by mass of an accelerator, 15 parts by mass of bismaleimide diphenyl methyl ether (OBMI) or Bismaleimide Diphenylmethane (BDM) and 56 parts by mass of a filler in an appropriate amount of an organic solvent to prepare a prepreg with the solid content of 66%, taking out a glass fiber cloth after soaking in the prepreg, and heating and drying at the temperature of 158 ℃ for 1.5min to obtain the prepreg; laminating 6 layers of prepregs, attaching copper foils on two sides, placing the prepregs in a hot press, placing the prepregs in the hot press at 165 ℃, pressurizing to 1MPa (according to the condition of the flow adhesive), laminating for 0.6h, gradually heating to 230 ℃, hot-pressing for 3.5h, and naturally cooling to obtain the high-heat-resistance low-dielectric active ester resin laminated board.
The definition of the prepreg with 66% solid content is: 100g of the prepreg was baked in an oven at 125 ℃ for 3 hours, and the mass of the non-volatile matter accounted for 66% of the total mass, and the amount of solid finally determined by mass blending of the added solvent was calculated based on the mass of the non-volatile matter.
Example 12:
a preparation method of a high-heat-resistance low-dielectric-activity ester resin laminated board comprises the following steps: uniformly dispersing a high-heat-resistance low-dielectric resin composition containing 100 parts by mass of active ester type maleimide resin, 40-80 parts by mass of any epoxy resin, 0.2-0.6 part by mass of any accelerator, 10-25 parts by mass of bismaleimide diphenyl methyl ether (OBMI) or Bismaleimide Diphenylmethane (BDM) and 45-76 parts by mass of any filler in an appropriate amount of organic solvent to prepare a prepreg with solid content of 60-70%, dipping glass fiber cloth in the prepreg, taking out the prepreg, and heating and drying at any temperature of 150-170 ℃ for 1-4 min to obtain the prepreg; overlapping any one of the prepregs 3-16, attaching copper foils on two surfaces of the prepregs, placing the prepregs in a hot press at any temperature of 160-170 ℃, pressurizing to any one of 0.2-4 MPa (according to the condition of the flow adhesive, gradually) pressing for any one of 0.5-1 h, gradually heating to any one of 180-250 ℃, carrying out hot pressing for any one of 3-5 h, and naturally cooling to obtain the high-heat-resistance low-dielectric-activity ester resin laminated board.
The definition of the prepreg with the solid content of 60-70% is as follows: 100g of the prepreg was baked in an oven at 125 ℃ for 3 hours, and the mass of the non-volatile matter was calculated as a percentage of the total mass, and the amount of solid finally determined by the mass blending of the added solvent was calculated based on the mass of the non-volatile matter.
In the above embodiments 8 to 12: the organic solvent is any one of acetone, butanone, methyl isobutyl ketone, propylene glycol monomethyl ether and ethylene glycol methyl ether.
In the above embodiments 4 to 12:
the active ester type maleimide resin is a maleimide resin containing two or more active ester group structures; the active ester type maleimide resin may be any one of polyester type maleimide resin (self-made), dicyclopentadiene phenol ester type maleimide resin (self-made), novolak type maleimide resin (for example, phenol novolak type maleimide resin, o-cresol novolak ester type maleimide resin, phenol aralkyl novolak type maleimide resin, bisphenol A novolak type maleimide resin, etc.) (self-made);
the epoxy resin is an aromatic compound containing two or more epoxy groups, and can be any one of bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin (phenol formaldehyde novolac type epoxy resin, o-cresol formaldehyde novolac type epoxy resin, bisphenol A formaldehyde novolac type epoxy resin) and dicyclopentadiene phenol type epoxy resin; the production and supply enterprises of epoxy resin products are as follows: jinan Shengquan group, Inc., Jiannshengde materials science and technology, Inc., Wuxi Lanxing petrochemical, Inc., Nanya New materials science and technology, Inc., Shenzhen Jia Dida New materials science and technology, Inc., etc.;
the accelerant is any one of 2,4, 6-tri (dimethylaminomethyl) phenol (DMP-30 for short), triphenylphosphine (TPP for short), 4-dimethylaminopyridine, 2-methylimidazole, 1-benzyl-2-methylimidazole and the like;
the filler is any one of silicon dioxide, montmorillonite, magnesium oxide, aluminum oxide, mica powder and the like;
in the above embodiments 4 to 12:
the polyester maleimide resin is a compound having a general chemical structure represented by formula (1):
Figure BDA0002222970570000181
in formula (1): m is 2 to 4, Ar1And Ar2The aromatic group can be phenyl, naphthyl, biphenyl and the groups which are substituted by C1-C3 alkyl, alkoxy, halogen and the like; the R group is phenyl or alkyl group with 2-5 carbon atoms;
the dicyclopentadiene phenol ester type maleimide resin is a compound having a general chemical structure represented by formula (2):
Figure BDA0002222970570000191
in formula (2): n is 1 to 3, and X is
Figure BDA0002222970570000192
The novolak type maleimide resin is a compound having a general chemical structure represented by the formula (3-1, 3-2 or 3-3):
Figure BDA0002222970570000193
a phenol novolac maleimide resin and a mono-substituted phenol novolac maleimide resin of formula (3-1) (e.g., an o-cresol novolac maleimide resin and an m-cresol novolac maleimide resin), wherein in formula (3-1), k is 1 to 3, and X is
Figure BDA0002222970570000194
Y is C1-C3 alkyl, C1-C3 alkoxy, chlorine, bromine, fluorine and the like;
Figure BDA0002222970570000195
a phenol aralkyl novolak type maleimide resin of the formula (3-2) wherein: j is 1 to 3, and X is
Figure BDA0002222970570000201
Figure BDA0002222970570000202
A bisphenol A novolac type maleimide resin of the formula (3-3), wherein: g is 1 to 3, and X is
Figure BDA0002222970570000203
In the above embodiments 4 to 12: the preparation of the polyester maleimide resin is carried out by reacting aromatic dihydric phenol, esterifying agent, end-capping agent and alkaline catalyst in organic solvent.
In the above embodiments 4 to 12: the specific preparation method of the polyester maleimide resin can be as follows: dissolving 0.4mol of aromatic dihydric phenol and 0.24mol of esterifying agent in 650 parts by mass of organic solvent, reacting for 3h at 50 ℃ under the action of 0.22mol of alkaline catalyst, adding 0.23mol of end-capping agent, continuing to react for 2h, filtering and washing to neutrality after the reaction is finished, and removing the organic solvent by reduced pressure distillation to obtain the polyester maleimide resin.
In the above embodiments 4 to 12: the specific preparation method of the polyester maleimide resin can be as follows: dissolving 0.4mol of aromatic dihydric phenol and 0.32mol of esterifying agent in 950 parts by mass of organic solvent, reacting for 2h at the temperature of 80 ℃ under the action of 0.68mol of basic catalyst, then adding 0.38mol of end-capping agent, continuing to react for 3h, filtering and washing to neutrality after the reaction is finished, and removing the organic solvent by reduced pressure distillation to obtain the polyester maleimide resin.
In the above embodiments 4 to 12: the specific preparation method of the polyester maleimide resin can be as follows: dissolving 0.4mol of aromatic dihydric phenol and 0.28mol of esterifying agent in 800 parts by mass of organic solvent, reacting for 2.5h at 75 ℃ under the action of 0.45mol of alkaline catalyst, then adding 0.31mol of end-capping agent, continuing to react for 2.5h, filtering and washing to neutrality after the reaction is finished, and removing the organic solvent by reduced pressure distillation to obtain the polyester maleimide resin.
In the above embodiments 4 to 12: the specific preparation method of the polyester maleimide resin can be as follows: dissolving 0.4mol of aromatic dihydric phenol and 0.24mol to 0.32mol of esterifying agent in 650 to 950 parts by mass of organic solvent, reacting for 2 to 3 hours at the temperature of 50 to 80 ℃ under the action of 0.22 to 0.68mol of alkaline catalyst, then adding 0.23 to 0.38mol of end capping agent, continuing to react for 2 to 3 hours, filtering and washing to be neutral after the reaction is finished, and removing the organic solvent by reduced pressure distillation to prepare the polyester maleimide resin.
The specific preparation method of the polyester maleimide resin comprises the following steps:
the aromatic dihydric phenol is one or a mixture of two of aromatic phenol compounds such as catechol, resorcinol, hydroquinone, 1, 4-naphthalenediol, 2, 6-naphthalenediol, 2 '-biphenyldiol and 4,4' -biphenyldiol, and aromatic phenol compounds obtained by substituting the aromatic phenol compounds (namely the aromatic phenol compounds) with C1-C3 alkyl, alkoxy, halogen and the like;
the esterifying agent is aromatic dibasic acid or anhydride such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic anhydride, 4-chloro-1, 8-naphthalenedicarboxylic anhydride, 2' -biphenyldicarboxylic acid, 4' -biphenyldicarboxylic acid, 2' -biphenyldicarboxylic anhydride, etc., and aromatic acid chloride compounds such as phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, 1, 4-naphthalenedicarboxylic acid chloride, 2, 6-naphthalenedicarboxylic acid chloride, 2 '-biphenyldicarbonyl chloride, 4' -biphenyldicarbonyl chloride, and one or a mixture of two of the above aromatic compounds which are mono-substituted with a C1-C3 alkyl group, an alkoxy group, a halogen or the like;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide (DMF for short), dimethylacetamide (DMAc for short) and N-methylpyrrolidone (NMP for short).
In the above embodiments 4 to 12: the dicyclopentadiene phenol ester type maleimide resin is prepared by reacting dicyclopentadiene phenol, a blocking agent and an alkaline catalyst in an organic solvent.
In the above embodiments 4 to 12: the specific preparation method of the dicyclopentadiene phenol ester type maleimide resin can be as follows: dissolving 100 parts by mass of dicyclopentadiene phenol and 164 parts by mass of end-capping reagent in 500 parts by mass of organic solvent, reacting for 3 hours at 50 ℃ under the action of 17 parts by mass of alkaline catalyst, filtering, washing to neutrality, and removing the organic solvent by reduced pressure distillation to obtain the dicyclopentadiene phenol ester type maleimide resin.
In the above embodiments 4 to 12: the specific preparation method of the dicyclopentadiene phenol ester type maleimide resin can be as follows: dissolving 100 parts by mass of dicyclopentadiene phenol and 308 parts by mass of an end-capping reagent in 1000 parts by mass of an organic solvent, reacting at 80 ℃ for 2 hours under the action of 116 parts by mass of an alkaline catalyst, filtering, washing with water to neutrality, and distilling to remove the organic solvent to obtain the dicyclopentadiene phenol ester type maleimide resin.
In the above embodiments 4 to 12: the specific preparation method of the dicyclopentadiene phenol ester type maleimide resin can be as follows: dissolving 100 parts by mass of dicyclopentadiene phenol and 237 parts by mass of end-capping reagent in 750 parts by mass of organic solvent, reacting at 75 ℃ for 2.5h under the action of 66 parts by mass of alkaline catalyst, filtering, washing with water to neutrality, and distilling to remove the organic solvent to obtain the dicyclopentadiene phenol ester type maleimide resin.
In the above embodiments 4 to 12: the specific preparation method of the dicyclopentadiene phenol ester type maleimide resin can be as follows: dissolving 100 parts by mass of dicyclopentadiene phenol and 164-308 parts by mass of an end-capping reagent in 500-1000 parts by mass of an organic solvent, reacting at 50-80 ℃ for 2-3 h under the action of 17-116 parts by mass of an alkaline catalyst, filtering, washing with water to neutrality, and distilling to remove the organic solvent to obtain the dicyclopentadiene phenol ester type maleimide resin.
The specific preparation method of the dicyclopentadiene phenol ester type maleimide resin comprises the following steps:
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide (DMF for short), dimethylacetamide (DMAc for short) and N-methylpyrrolidone (NMP for short).
In the above embodiments 4 to 12: the novolak type maleimide resin (e.g., phenol novolak type maleimide resin, orthocresol novolak type maleimide resin, phenol aralkyl novolak type maleimide resin, bisphenol A novolak type maleimide resin, etc.) is obtained by reacting a novolak resin, a capping agent, and an alkaline catalyst in an organic solvent.
In the above embodiments 4 to 12: the specific preparation method of the novolac phenolic ester maleimide resin can be as follows: dissolving 100 parts by mass of novolac resin and 164 parts by mass of end-capping reagent in 500 parts by mass of organic solvent, reacting for 3 hours at 50 ℃ under the action of 17 parts by mass of alkaline catalyst, filtering, washing to neutrality, and distilling under reduced pressure to remove the organic solvent to obtain the novolac ester type maleimide resin.
In the above embodiments 4 to 12: the specific preparation method of the novolac phenolic ester maleimide resin can be as follows: dissolving 100 parts by mass of novolac resin and 308 parts by mass of end-capping reagent in 1000 parts by mass of organic solvent, reacting for 2 hours at 80 ℃ under the action of 116 parts by mass of alkaline catalyst, filtering, washing to neutrality, and distilling under reduced pressure to remove the organic solvent to obtain the novolac ester type maleimide resin.
In the above embodiments 4 to 12: the specific preparation method of the novolac phenolic ester maleimide resin can be as follows: dissolving 100 parts by mass of novolac resin and 238 parts by mass of end-capping reagent in 750 parts by mass of organic solvent, reacting for 3 hours at 70 ℃ under the action of 67 parts by mass of alkaline catalyst, filtering, washing with water to neutrality, and distilling under reduced pressure to remove the organic solvent to obtain the novolac ester type maleimide resin.
In the above embodiments 4 to 12: the specific preparation method of the novolac phenolic ester maleimide resin can be as follows: dissolving 100 parts by mass of novolac resin and 164-308 parts by mass of end-capping reagent in 500-1000 parts by mass of organic solvent, reacting at 50-80 ℃ for 2-3 h under the action of 17-116 parts by mass of alkaline catalyst, filtering, washing to neutrality, and distilling under reduced pressure to remove the organic solvent to obtain the novolac maleimide resin.
The specific preparation method of the novolac phenolic ester type maleimide resin comprises the following steps:
the linear phenolic resin is any one of phenol type phenolic resin, o-cresol phenolic resin, m-cresol phenolic resin, bisphenol A formaldehyde resin and phenol aralkyl phenolic resin;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide (DMF for short), dimethylacetamide (DMAc for short) and N-methylpyrrolidone (NMP for short).
The high heat-resistant low dielectric active ester resin laminated board prepared in the above embodiments 8 to 12 has excellent comprehensive performance, and the related technical performance parameters are as follows: a glass transition temperature Tg of 241-257 ℃, a water absorption of 0.15-0.25%, a dielectric constant Dk of 3.49-3.75 at 10GHz, and a dielectric loss Df of 0.005-0.007.
In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the proportions used, not specifically noted, are mass (weight) proportions; the parts by weight may each be grams or kilograms.
In the above embodiment: the process parameters (temperature, time, concentration, pressure, etc.) and the amounts of the components in each step are within the range, and any point can be applicable.
The present invention and the technical contents not specifically described in the above examples are the same as those of the prior art, and the raw materials are all commercially available products.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.

Claims (8)

1. A high heat-resistant low-dielectric active ester resin composition is characterized in that: the high heat-resistant low-dielectric active ester resin composition is prepared by mixing 100 parts by mass of active ester maleimide resin, 40-80 parts by mass of epoxy resin, 0.2-0.6 part by mass of accelerator, 10-25 parts by mass of bismaleimide diphenyl methyl ether or bismaleimide diphenylmethane and 45-76 parts by mass of filler;
the active ester type maleimide resin is any one of polyester type maleimide resin, dicyclopentadiene phenol ester type maleimide resin and novolac phenolic ester type maleimide resin;
the promoter is any one of 2,4, 6-tri (dimethylaminomethyl) phenol, triphenylphosphine, 4-dimethylaminopyridine, 2-methylimidazole and 1-benzyl-2-methylimidazole;
the filler is any one of silicon dioxide, montmorillonite, magnesium oxide, aluminum oxide and mica powder;
the polyester maleimide resin is a compound having a general chemical structure represented by formula (1):
Figure FDA0003403754530000011
in formula (1): m is 2 to 4, Ar1And Ar2Is an aromatic group, such as phenyl, naphthyl, biphenyl and the groups which are substituted by C1-C3 alkyl, alkoxy and halogen; the R group is phenyl or alkyl with 2-5 carbon atoms;
the dicyclopentadiene phenol ester type maleimide resin is a compound having a general chemical structure represented by formula (2):
Figure FDA0003403754530000012
in formula (2): n is 1 to 3, and X is
Figure FDA0003403754530000021
The novolak type maleimide resin is a compound having a general chemical structure represented by the formula (3-1, 3-2 or 3-3):
Figure FDA0003403754530000022
a phenol novolac maleimide resin of the formula (3-1) wherein k is 1 to 3 and X is a mono-substituted phenol novolac maleimide resin
Figure FDA0003403754530000023
Y is C1-C3 alkyl, C1-C3 alkoxy, chlorine, bromine or fluorine;
Figure FDA0003403754530000024
a phenol aralkyl novolak type maleimide resin of the formula (3-2) wherein: j is 1 to 3, and X is
Figure FDA0003403754530000025
Figure FDA0003403754530000026
Figure FDA0003403754530000031
A bisphenol A novolac type maleimide resin of the formula (3-3), wherein: g is 1 to 3, and X is
Figure FDA0003403754530000032
2. The high heat resistance, low dielectric active ester resin composition as claimed in claim 1, wherein: the specific preparation method of the polyester maleimide resin comprises the following steps: dissolving 0.4mol of aromatic dihydric phenol and 0.24mol to 0.32mol of esterifying agent in 650 to 950 parts by mass of organic solvent, reacting for 2 to 3 hours at the temperature of 50 to 80 ℃ under the action of 0.22 to 0.68mol of alkaline catalyst, then adding 0.23 to 0.38mol of end capping agent, continuing to react for 2 to 3 hours, filtering and washing to be neutral after the reaction is finished, and removing the organic solvent through reduced pressure distillation to prepare the polyester maleimide resin;
the aromatic dihydric phenol is one or a mixture of two of catechol, resorcinol, hydroquinone, 1, 4-naphthalenediol, 2, 6-naphthalenediol, 2 '-biphenyldiol, 4' -biphenyldiol and aromatic phenol compounds which are substituted by C1-C3 alkyl, alkoxy and halogen;
the esterifying agent is one or a mixture of two of phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic anhydride, 2' -biphenyldicarboxylic acid, 4' -biphenyldicarboxylic acid, 2' -biphenyldicarboxylic anhydride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, 1, 4-naphthalenedicarboxylic chloride, 2, 6-naphthalenedicarboxylic chloride, 2' -biphenyldicarboxylic chloride, 4' -biphenyldicarboxylic chloride and the aromatic compounds which are substituted by C1-C3 alkyl, alkoxy and halogen;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
3. The high heat resistance, low dielectric active ester resin composition as claimed in claim 1, wherein: the specific preparation method of the dicyclopentadiene phenol ester type maleimide resin comprises the following steps: dissolving 100 parts by mass of dicyclopentadiene phenol and 164-308 parts by mass of an end-capping reagent in 500-1000 parts by mass of an organic solvent, reacting at 50-80 ℃ for 2-3 h under the action of 17-116 parts by mass of an alkaline catalyst, filtering, washing to neutrality, and distilling under reduced pressure to remove the organic solvent to obtain dicyclopentadiene phenol ester type maleimide resin;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
4. The high heat resistance, low dielectric active ester resin composition as claimed in claim 1, wherein: the specific preparation method of the novolac phenolic ester maleimide resin comprises the following steps: dissolving 100 parts by mass of novolac resin and 164-308 parts by mass of end-capping reagent in 500-1000 parts by mass of organic solvent, reacting at 50-80 ℃ for 2-3 h under the action of 17-116 parts by mass of alkaline catalyst, filtering, washing with water to neutrality, and distilling under reduced pressure to remove the organic solvent to obtain novolac ester type maleimide resin;
the linear phenolic resin is any one of phenol type phenolic resin, o-cresol phenolic resin, m-cresol phenolic resin, bisphenol A formaldehyde resin and phenol aralkyl phenolic resin;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
5. A preparation method of a high-heat-resistance low-dielectric-activity ester resin laminated board is characterized by comprising the following steps: uniformly dispersing a high-heat-resistance low-dielectric resin composition containing 100 parts by mass of active ester type maleimide resin, 40-80 parts by mass of epoxy resin, 0.2-0.6 part by mass of an accelerator, 10-25 parts by mass of bismaleimide diphenyl methyl ether or bismaleimide diphenylmethane and 45-76 parts by mass of a filler in an organic solvent to prepare a prepreg with the solid content of 60-70%, taking out a glass fiber cloth after dipping in the prepreg, and heating and drying at the temperature of 150-170 ℃ for 1-4 min to obtain a prepreg; stacking 3-16 prepregs, attaching copper foils to two surfaces of the prepregs, placing the prepregs in a hot press at 160-170 ℃, pressurizing to 0.2-4 MPa, laminating for 0.5-1 h, gradually heating to 180-250 ℃, hot-pressing for 3-5 h, and naturally cooling to obtain the high-heat-resistance low-dielectric active ester resin laminated board;
the active ester type maleimide resin is any one of polyester type maleimide resin, dicyclopentadiene phenol ester type maleimide resin and novolac phenolic ester type maleimide resin;
the promoter is any one of 2,4, 6-tri (dimethylaminomethyl) phenol, triphenylphosphine, 4-dimethylaminopyridine, 2-methylimidazole and 1-benzyl-2-methylimidazole;
the filler is any one of silicon dioxide, montmorillonite, magnesium oxide, aluminum oxide and mica powder;
the organic solvent is any one of acetone, butanone, methyl isobutyl ketone, propylene glycol monomethyl ether and ethylene glycol methyl ether;
the polyester maleimide resin is a compound having a general chemical structure represented by formula (1):
Figure FDA0003403754530000051
in formula (1): m is 2 to 4, Ar1And Ar2Is an aromatic group, such as phenyl, naphthyl, biphenyl and the groups which are substituted by C1-C3 alkyl, alkoxy and halogen; the R group is phenyl or alkyl with 2-5 carbon atoms;
the dicyclopentadiene phenol ester type maleimide resin is a compound having a general chemical structure represented by formula (2):
Figure FDA0003403754530000052
in formula (2): n is 1 to 3, and X is
Figure FDA0003403754530000053
The novolak type maleimide resin is a compound having a general chemical structure represented by the formula (3-1, 3-2 or 3-3):
Figure FDA0003403754530000061
a phenol novolac maleimide resin of the formula (3-1) wherein k is 1 to 3 and X is a mono-substituted phenol novolac maleimide resin
Figure FDA0003403754530000062
Y is C1-C3 alkyl, C1-C3 alkoxy, chlorine, bromine or fluorine;
Figure FDA0003403754530000063
a phenol aralkyl novolak type maleimide resin of the formula (3-2) wherein: j is 1 to 3, and X is
Figure FDA0003403754530000064
Figure FDA0003403754530000065
A bisphenol A novolac type maleimide resin of the formula (3-3), wherein: g is 1 to 3, and X is
Figure FDA0003403754530000071
6. The method for preparing a high heat resistance low dielectric active ester resin laminate as claimed in claim 5, wherein: the specific preparation method of the polyester maleimide resin comprises the following steps: dissolving 0.4mol of aromatic dihydric phenol and 0.24mol to 0.32mol of esterifying agent in 650 to 950 parts by mass of organic solvent, reacting for 2 to 3 hours at the temperature of 50 to 80 ℃ under the action of 0.22 to 0.68mol of alkaline catalyst, then adding 0.23 to 0.38mol of end capping agent, continuing to react for 2 to 3 hours, filtering and washing to be neutral after the reaction is finished, and removing the organic solvent through reduced pressure distillation to prepare the polyester maleimide resin;
the aromatic dihydric phenol is one or a mixture of two of catechol, resorcinol, hydroquinone, 1, 4-naphthalenediol, 2, 6-naphthalenediol, 2 '-biphenyldiol, 4' -biphenyldiol and aromatic phenol compounds which are substituted by C1-C3 alkyl, alkoxy and halogen;
the esterifying agent is one or a mixture of two of phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic anhydride, 2' -biphenyldicarboxylic acid, 4' -biphenyldicarboxylic acid, 2' -biphenyldicarboxylic anhydride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, 1, 4-naphthalenedicarboxylic chloride, 2, 6-naphthalenedicarboxylic chloride, 2' -biphenyldicarboxylic chloride, 4' -biphenyldicarboxylic chloride and the aromatic compounds which are substituted by C1-C3 alkyl, alkoxy and halogen;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
7. The method for preparing a high heat resistance low dielectric active ester resin laminate as claimed in claim 5, wherein: the specific preparation method of the dicyclopentadiene phenol ester type maleimide resin comprises the following steps: dissolving 100 parts by mass of dicyclopentadiene phenol and 164-308 parts by mass of an end-capping reagent in 500-1000 parts by mass of an organic solvent, reacting at 50-80 ℃ for 2-3 h under the action of 17-116 parts by mass of an alkaline catalyst, filtering, washing to neutrality, and distilling under reduced pressure to remove the organic solvent to obtain dicyclopentadiene phenol ester type maleimide resin;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
8. The method for preparing a high heat resistance low dielectric active ester resin laminate as claimed in claim 5, wherein: the specific preparation method of the novolac phenolic ester maleimide resin comprises the following steps: dissolving 100 parts by mass of novolac resin and 164-308 parts by mass of end-capping reagent in 500-1000 parts by mass of organic solvent, reacting at 50-80 ℃ for 2-3 h under the action of 17-116 parts by mass of alkaline catalyst, filtering, washing with water to neutrality, and distilling under reduced pressure to remove the organic solvent to obtain novolac ester type maleimide resin;
the linear phenolic resin is any one of phenol type phenolic resin, o-cresol phenolic resin, m-cresol phenolic resin, bisphenol A formaldehyde resin and phenol aralkyl phenolic resin;
the end-capping reagent is any one of 4-maleimide benzoic acid, 3-maleimide propionic acid, 6-maleimide caproic acid and acyl chloride compounds thereof;
the alkaline catalyst is any one of potassium hydroxide, sodium hydroxide, pyridine and triethylamine;
the organic solvent is any one of toluene, xylene, dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
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