Twisted non-planar-configuration bismaleimide, laminated board and preparation method thereof
阅读说明：本技术 一种扭曲非平面构型双马来酰亚胺、用于层压板及其制备方法 (Twisted non-planar-configuration bismaleimide, laminated board and preparation method thereof ) 是由 漆志刚 毛华 周友 宋贤锋 唐安斌 于 2021-08-16 设计创作，主要内容包括：本发明公开了式(Ⅰ)所示的扭曲非平面构型双马来酰亚胺、用于层压板及其制备方法,扭曲非平面构型双马来酰亚胺的制备方法是：将茚满类芳香二胺与溶剂混合溶解,滴加入溶于溶剂的顺丁烯二酸酐溶液,加入乙酸酐、催化剂,在60～70～(o)C反应4～5h,冷却,用水沉析,过滤,重结晶即制得。将扭曲非平面构型双马来酰亚胺、氰酸酯、环氧树脂、烯丙基酚类化合物、氧化氢二异丙基苯、固化促进剂、无机填料和溶剂混合得组合料液,将增强材料浸渍后取出烘烤,制得半固化片；半固化片的两侧附上金属铜箔,置于真空热压机中,在一定压力和温度下压合,制得层压板。本发明适用于耐热性、耐湿性等复合材料树脂基体、电子封装基板材料等领域,实用性强。 (I)。(The invention discloses distorted non-planar configuration bismaleimide shown as a formula (I), a laminated board and a preparation method thereof, wherein the preparation method of the distorted non-planar configuration bismaleimide comprises the following steps: mixing and dissolving indane aromatic diamine and a solvent, dripping a maleic anhydride solution dissolved in the solvent, adding acetic anhydride and a catalyst, and reacting at 60-70 DEG C o C, reacting for 4-5 h, cooling, precipitating with water, filtering, and recrystallizing to obtain the product. Will distort out of planeMixing the configured bismaleimide, cyanate ester, epoxy resin, allyl phenolic compound, hydrogen peroxide diisopropylbenzene, curing accelerator, inorganic filler and solvent to obtain a combined feed liquid, soaking the reinforcing material, taking out and baking to obtain a prepreg; attaching metal copper foils on two sides of the prepreg, placing the prepreg in a vacuum hot press, and pressing the prepreg at a certain pressure and temperature to obtain the laminated board. The invention is suitable for the fields of composite material resin matrix, electronic packaging substrate material and the like with heat resistance, moisture resistance and the like, and has strong practicability.)
1. A distorted non-planar configuration bismaleimide, which is characterized in that: the distorted non-planar bismaleimide has a chemical structural general formula shown in a formula (I):
in formula (I): r1Halogen such as hydrogen, methyl, chlorine or bromine or an alkyl group having 1 to 8 carbon atoms; r2Is hydrogen or an alkyl group having 1 to 8 carbon atoms, and X is any one of-CO-O-, -S-, -O-or-CO-NH-.
2. A preparation method of bismaleimide with a distorted non-planar configuration is characterized by comprising the following steps:
a. adding indane aromatic diamine into a reaction kettle, adding an organic solvent, and stirring to dissolve the indane aromatic diamine;
b. dissolving maleic anhydride in an organic solvent, dropwise adding the solution into a reaction kettle within 2-2.5 h, and continuously stirring for 3-4 h after dropwise adding is finished;
c. adding acetic anhydride and a catalyst, heating to 60-70 ℃, and carrying out heat preservation reaction for 4-5 h;
d. cooling, precipitating with water, filtering, and recrystallizing the obtained solid with toluene to obtain bismaleimide with distorted non-planar configuration.
3. The method for preparing distorted non-planar bismaleimide as claimed in claim 2, wherein the method comprises the steps of:
a. adding 0.08mol of indane aromatic diamine into a reaction kettle, adding 100ml of organic solvent, and stirring to dissolve the indane aromatic diamine;
b. dissolving 0.20mol of maleic anhydride in 150ml of organic solvent, dropwise adding into the reaction kettle within 2-2.5 h, and continuously stirring for 3-4 h after dropwise adding is finished;
c. adding 0.22mol of acetic anhydride and 0.001mol of catalyst, heating to 60-70 ℃, and reacting for 4-5 hours in a heat preservation manner;
d. cooling, precipitating with water, filtering, and recrystallizing the obtained solid with toluene to obtain bismaleimide with distorted non-planar configuration.
4. A process for the preparation of distorted non-planar bismaleimides according to claim 2 or 3, characterized by: the indane aromatic diamine in the step a is any one or any combination of indane structure-containing aromatic diamine compounds containing isomers or substituted isomers.
5. A process for the preparation of distorted non-planar bismaleimides according to claim 2 or 3, characterized by: the indane aromatic diamine may be specifically one or a mixture of two or more of 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindane, 5(6) - (4-aminobenzamido) -1- (4-aminobenzamido) phenyl-1, 3, 3-trimethylindane, 5(6) - (4-aminophenoxy) -1- (4-aminophenoxy) phenyl-1, 3, 3-trimethylindane, and 5(6) - (4-aminobenzoyloxy) -1- (4-aminobenzoyloxy) phenyl-1, 3, 3-trimethylindane.
6. A process for the preparation of distorted non-planar bismaleimides according to claim 2 or 3, characterized by: in the step a and the step b, the organic solvent is one or a mixture of more than two of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and acetone.
7. A process for the preparation of distorted non-planar bismaleimides according to claim 2 or 3, characterized by: in the step c, the catalyst is one or a mixture of more than two of sodium acetate, nickel acetate, cobalt acetate and magnesium acetate.
8. A method for preparing a laminated board by using bismaleimide with a distorted non-planar configuration is characterized by comprising the following steps:
a. stirring 100 parts by mass of distorted non-planar bismaleimide, 10-100 parts by mass of cyanate ester, 0-40 parts by mass of epoxy resin and 0-20 parts by mass of allyl phenolic compound at the temperature of 100-180 ℃, then adding 0.3-1.0 part by mass of hydrogen peroxide diisopropylbenzene, 0.1-0.5 part by mass of curing accelerator, 15-85 parts by mass of inorganic filler and a solvent at the temperature of 50-100 ℃, uniformly mixing to obtain a combined feed liquid, putting a reinforcing material into the combined feed liquid for dipping, taking out, and baking at the temperature of 120-185 ℃ for 1-10 min to obtain a prepreg;
b. attaching metal copper foils to two sides of a prepreg, cutting and overlapping according to the requirements of length, width and thickness, placing the prepreg in a vacuum hot press, keeping the temperature rise rate of 1-3 ℃/min from room temperature to 100-180 ℃, keeping the prepreg pressed for 1-3 hours under the pressure of 0.3-1 MPa and the temperature of 100-180 ℃, then keeping the prepreg pressed for 1-3 hours, keeping the prepreg pressed for 180-250 ℃ under the temperature rise rate of 1-3 ℃/min, and pressing for 1-5 hours under the pressure of 3-8 MPa and the temperature of 180-250 ℃ to obtain the laminated board containing the twisted non-planar bismaleimide.
9. The process for producing a laminate using the distorted non-planar bismaleimide as claimed in claim 7 wherein: the step a is as follows: stirring 100 parts by mass of distorted non-planar bismaleimide, 10-100 parts by mass of cyanate ester, 20-40 parts by mass of epoxy resin and 5-20 parts by mass of allyl phenolic compound at the temperature of 100-180 ℃, then adding 0.3-1.0 part by mass of hydrogen peroxide diisopropylbenzene, 0.1-0.5 part by mass of curing accelerator, 15-85 parts by mass of inorganic filler and solvent at the temperature of 50-100 ℃, uniformly mixing to obtain a combined feed liquid, putting the reinforcing material into the combined feed liquid for dipping, taking out, and baking at the temperature of 120-185 ℃ for 1-10 min to obtain a prepreg.
10. A process for the preparation of a laminate from the distorted non-planar configuration of bismaleimides as claimed in claim 7 or 8, characterized by: in the step a:
the cyanate is any one of bisphenol A cyanate, bisphenol M cyanate, bisphenol F cyanate, tetramethyl bisphenol F cyanate, phenolic cyanate and cyclopentadiene cyanate;
the epoxy resin is one or a mixture of more than two of bisphenol A type epoxy resin and novolac epoxy resin;
the allyl phenolic compound is any one of diallyl bisphenol A, allyl phenol and 2, 2' -diallyl bisphenol A;
the curing accelerator is any one of imidazole compounds, acetylacetone transition metal complexes and carboxylic acid compounds;
the inorganic filler is one or a mixture of more than two of magnesium hydroxide, calcium carbonate, aluminum hydroxide, silicon dioxide, silicon micropowder, hollow glass beads and gas-phase silicon dioxide;
the solvent is one or a mixture of more than two of butanone, toluene, xylene, acetone, propylene glycol monomethyl ether and N, N-dimethylformamide;
the reinforcing material is any one of organic synthetic fiber, organic fabric, natural fiber and inorganic fabric.
Technical Field
The invention belongs to an organic compound, a laminated board and preparation thereof, and relates to distorted non-planar configuration bismaleimide, a laminated board and a preparation method thereof. The (prepared) distorted non-planar bismaleimide provided by the invention is suitable for the fields of heat resistance, moisture resistance and the like of composite material resin matrixes, electronic packaging substrate materials and the like.
Background
In the current electronic and electrical market, the power of components is getting larger and the integration density is getting higher, the requirement for heat resistance is improved, and meanwhile, the use of lead-free solder needs higher glass transition temperature and thermal stability of a substrate material for packaging. The mobile electronic equipment such as mobile phones and the like is widely used, and the electronic equipment is carried and applied in the peripheral environment and the position close to the human body, so that the components and parts have higher requirements on the external environment, particularly on the humidity and heat resistance. In addition, with the rapid development in the field of automotive electronics, electronic devices are required to cope with higher levels of heat resistance and moisture resistance.
At present, the traditional epoxy resin system can not meet the requirements of high heat resistance, low water absorption and the like required by the processing of high-performance packaging substrates of integrated circuits and the design and use of electronic components. In the prior art, bismaleimide resin-cyanate ester composite resin (BT resin for short) is a thermosetting resin, has good heat resistance, electrical insulation, ion migration resistance, chemical corrosion resistance and dimensional stability, and is used by adjusting the ratio of bismaleimide to cyanate ester components to adjust the glass transition temperature, dielectric constant and other properties of the composite resin. However, the solubility of the currently commercialized bismaleimides such as N, N-4, 4' -diphenylmethane Bismaleimide (BDM) and N, N-m-phenylene bismaleimide (PDM) is poor, the BT resin prepared therefrom is poor in solubility, and the processing condition control difficulty is high.
Disclosure of Invention
The present invention aims to overcome the defects in the prior art and provide bismaleimide with a distorted non-planar configuration, a bismaleimide used for a laminated board and a preparation method thereof. Thereby providing the distorted non-planar bismaleimide with good solubility, excellent toughness and humidity resistance, a laminated board and a preparation method thereof.
The content of the invention is as follows: a distorted non-planar configuration bismaleimide, which is characterized in that: the distorted non-planar bismaleimide has a chemical structural general formula shown in a formula (I):
in formula (I): r1Halogen such as hydrogen, methyl, chlorine or bromine or an alkyl group having 1 to 8 carbon atoms; r2Is hydrogen or an alkyl group having 1 to 8 carbon atoms, and X is any one of-CO-O-, -S-, -O-or-CO-NH-.
Another aspect of the invention is: a preparation method of bismaleimide with a distorted non-planar configuration is characterized by comprising the following steps:
a. adding indane aromatic diamine into a reaction kettle, adding a proper amount of organic solvent, and stirring to dissolve the indane aromatic diamine;
b. dissolving maleic anhydride (in a dosage ratio) in an organic solvent, dropwise adding the solution into a reaction kettle within 2-2.5 h, and continuously stirring for 3-4 h after dropwise adding is finished;
c. adding a certain amount of acetic anhydride and a catalyst, heating to 60-70 ℃, and carrying out heat preservation reaction for 4-5 hours;
d. cooling (after the reaction is finished), precipitating by using (a large amount of) water, filtering, and recrystallizing the obtained solid by using toluene to obtain the bismaleimide with the distorted non-planar configuration.
The invention also provides a preparation method of the distorted non-planar configuration bismaleimide, which is characterized by comprising the following steps:
a. adding 0.08mol of indane aromatic diamine into a reaction kettle, adding 100ml of organic solvent, and stirring to dissolve the indane aromatic diamine;
b. dissolving 0.20mol of maleic anhydride in 150ml of organic solvent, dropwise adding into the reaction kettle within 2-2.5 h, and continuously stirring for 3-4 h after dropwise adding is finished;
c. adding 0.22mol of acetic anhydride and 0.001mol of catalyst, heating to 60-70 ℃, and reacting for 4-5 hours in a heat preservation manner;
d. cooling (after the reaction is finished), precipitating by using (a large amount of) water, filtering, and recrystallizing the obtained solid by using toluene to obtain the bismaleimide with the distorted non-planar configuration.
In another aspect of the invention: the indane aromatic diamine in the step a can be any one or any combination of indane structure-containing aromatic diamine compounds containing isomers or substituted isomers; indane aromatic diamines are prepared as disclosed in US3856752 and US3983092, which are prior art.
In another aspect of the invention: the indane aromatic diamine may be specifically one or a mixture of two or more of 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindane, 5(6) - (4-aminobenzamido) -1- (4-aminobenzamido) phenyl-1, 3, 3-trimethylindane, 5(6) - (4-aminophenoxy) -1- (4-aminophenoxy) phenyl-1, 3, 3-trimethylindane, and 5(6) - (4-aminobenzoyloxy) -1- (4-aminobenzoyloxy) phenyl-1, 3, 3-trimethylindane.
In another aspect of the invention: the organic solvent in the step a and the step b can be one or a mixture of more than two of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and acetone;
in another aspect of the invention: in the step c, the catalyst can be one or a mixture of more than two of sodium acetate, nickel acetate, cobalt acetate and magnesium acetate.
Another aspect of the invention is: a method for preparing a laminated board by using bismaleimide with a distorted non-planar configuration is characterized by comprising the following steps:
a. stirring (uniformly) 100 parts by mass of distorted non-planar bismaleimide, 10-100 parts by mass of cyanate ester, 0-40 parts by mass of epoxy resin and 0-20 parts by mass of allyl phenolic compound at the temperature of 100-180 ℃, then adding 0.3-1.0 part by mass of hydrogen peroxide diisopropylbenzene, 0.1-0.5 part by mass of curing accelerator, 15-85 parts by mass of inorganic filler and a proper amount of solvent at the temperature of 50-100 ℃ and uniformly mixing to obtain a combined feed liquid, then placing a reinforcing material into the combined feed liquid (fully) for dipping and taking out, and baking at the temperature of 120-185 ℃ for 1-10 min to obtain a prepreg;
b. attaching metal copper foils to two sides of a prepreg, cutting and superposing the prepreg according to the length, width and thickness requirements, placing the prepreg in a vacuum hot press, keeping the temperature rise rate of 1-3 ℃/min from room temperature to 100-180 ℃, keeping the prepreg pressed for 1-3 hours under the pressure of 0.3-1 MPa and the temperature of 100-180 ℃, then keeping the prepreg pressed for 1-3 hours, keeping the prepreg pressed for 180-250 ℃ under the temperature rise rate of 1-3 ℃/min, and pressing the prepreg for 1-5 hours under the pressure of 3-8 MPa and the temperature of 180-250 ℃ to obtain the laminated board (or called as a damp-heat resistant laminated board) containing the distorted non-planar bismaleimide.
In another aspect of the invention: the step a is preferably: 100 parts by mass of distorted non-planar bismaleimide, 10-100 parts by mass of cyanate ester, 20-40 parts by mass of epoxy resin and 5-20 parts by mass of allyl phenolic compound are stirred (uniformly) at the temperature of 100-180 ℃, then 0.3-1.0 part by mass of hydrogen peroxide diisopropylbenzene, 0.1-0.5 part by mass of curing accelerator, 15-85 parts by mass of inorganic filler and a proper amount of solvent are added at the temperature of 50-100 ℃ and uniformly mixed to obtain a combined feed liquid, then the reinforcing material is placed in the combined feed liquid (fully) for dipping and then taken out, and the combined feed liquid is baked at the temperature of 120-185 ℃ for 1-10 min to obtain a prepreg.
In another aspect of the invention: the distorted non-planar configuration bismaleimide in the step a is obtained by the preparation;
the cyanate is any one of bisphenol A cyanate, bisphenol M cyanate, bisphenol F cyanate, tetramethyl bisphenol F cyanate, phenolic cyanate and cyclopentadiene cyanate;
the epoxy resin is one or a mixture of more than two of bisphenol A type epoxy resin (such as Shengquan SQP-40AXM40, great alignment DYD-115 and baring petrochemical E-44), phenolic epoxy resin (such as Shengquan SQPN-051, great alignment PGCN-701 and baring petrochemical CYDCN-200);
the allyl phenolic compound is any one of diallyl bisphenol A, allyl phenol and 2, 2' -diallyl bisphenol A;
the curing accelerator is any one of imidazole compounds (such as 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole formed by four countries) and acetylacetone transition metal complexes (such as cobalt acetylacetonate, zinc acetylacetonate and chromium acetylacetonate);
the inorganic filler is one or a mixture of more than two of magnesium hydroxide, calcium carbonate, aluminum hydroxide, silicon dioxide, silicon micropowder, hollow glass beads and gas-phase silicon dioxide;
the solvent is one or a mixture of more than two of butanone, toluene, xylene, acetone, propylene glycol monomethyl ether and N, N-dimethylformamide;
the reinforcing material is any one of organic synthetic fiber, organic fabric, natural fiber and inorganic fabric.
The thickness of the metal copper foil in the step b is not limited.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) by adopting the invention, the indane structure of the distorted non-planar bismaleimide makes the molecular chain difficult to adopt the straight linear configuration, the solubility is improved, the asymmetric distorted non-planar structure reduces the crystallization of the resin, the processing of the resin is facilitated, and meanwhile, the molecule contains a plurality of aromatic rings, so the heat resistance of the resin is improved;
(2) the distorted non-planar bismaleimide has good solubility, toughness and humidity resistance, is suitable for the fields of composite material resin matrix with high heat resistance, humidity resistance and the like, electronic packaging substrate materials and the like, and has good performance;
(3) the product of the invention has simple preparation process, simple and convenient working procedure, 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.
Synthesis (preparation) of bismaleimide with a first partially distorted non-planar configuration
Synthesis example 1:
5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindan (21.31g, 0.08mol) and 100ml of acetone were put into a four-necked flask equipped with a thermometer, a dropping funnel and a stirrer, and dissolved by stirring. Maleic anhydride (19.6g, 0.20mol) was dissolved in 150ml acetone, and then added dropwise to a four-necked flask via a dropping funnel over 2.5h, and stirring was continued for 4h after the addition was completed. Acetic anhydride (22.46, 0.22mol), sodium acetate (0.08g, 0.001mol) were then added and the temperature was raised to 60-70 ℃ and held for 4 h. Cooling, precipitating with a large amount of water, filtering, recrystallizing in toluene to obtain bismaleimide (hereinafter abbreviated as M1) with distorted non-planar configuration, and drying at 80 deg.C to obtain 75% yield. Melting point: 155 ℃ and 170 ℃ (measured by a melting point instrument).
The infrared structural characterization data are: FT-IR (KBr, cm)-1):3107cm-1(-CH＝CH-)；2932cm-1(-CH3)；1778、1762cm-1(C＝O)；1473cm-1(O＝C-N)。
Synthesis example 2:
in the same manner as in example 1 except that 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindan was changed to 5(6) - (4-aminobenzamido) -1- (4-aminobenzamido) phenyl-1, 3, 3-trimethylindan and acetone was changed to N, N-dimethylformamide, bismaleimide having a distorted non-planar configuration (hereinafter abbreviated as M2) was obtained in a yield of 70%. Melting point: 165 ℃ and 178 ℃ (melting point instrument measurement).
The infrared structural characterization data are: FT-IR (KBr, cm)-1):3117cm-1(-CH＝CH-)；2952cm-1(-CH3)；1771、1752cm-1(C＝O)；1463cm-1(O＝C-N)。
Synthesis example 3:
in the same manner as in example 1 except that 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindan was changed to 5(6) - (4-aminophenoxy) -1- (4-aminophenoxy) phenyl-1, 3, 3-trimethylindan, and sodium acetate was changed to nickel acetate, bismaleimide (hereinafter abbreviated as M3) having a distorted non-planar configuration was obtained in a yield of 68%. Melting point: 160 ℃ and 170 ℃ (as measured by a melting point instrument).
The infrared structural characterization data are: FT-IR (KBr, cm)-1):3007cm-1(-CH＝CH-)；2912cm-1(-CH3)；1768、1752cm-1(C＝O)；1471cm-1(O＝C-N)；1248(Ar-O)。
Synthesis example 4:
by changing 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindan to 5(6) - (4-aminobenzoyloxy) -1- (4-aminobenzoyloxy) phenyl-1, 3, 3-trimethylindan and replacing acetone with N-methylpyrrolidone, bismaleimide having a distorted non-planar configuration (hereinafter abbreviated as M4) was obtained in a yield of 62% in the same manner as in example 1 except that the other components were changed. Melting point: 165 ℃ and 178 ℃ (melting point instrument measurement).
The infrared structural characterization data are: FT-IR (KBr, cm)-1):3007cm-1(-CH＝CH-)；2912cm-1(-CH3)；1768、1752cm-1(C＝O)；1471cm-1(O＝C-N)；1288(C-O-C)。
The bismaleimide with twisted non-planar configuration prepared in synthesis examples 1 to 4 has good solubility and can be dissolved in most organic solvents.
Table 1: solubility of distorted non-planar configuration bismaleimide:
note: in the table, "+ +" indicates dissolution at room temperature, "+ -" indicates dissolution by heating, and "-" indicates no dissolution.
Second partially twisted non-planar bismaleimide for producing laminates
a. Preparing a combined feed liquid: stirring (uniformly) 100 parts by mass of distorted non-planar bismaleimide, 10-100 parts by mass of cyanate ester, 0-40 parts by mass of epoxy resin and 0-20 parts by mass of allyl phenolic compound at the temperature of 100-180 ℃, and then adding 0.3-1.0 part by mass of hydrogen peroxide diisopropylbenzene, 0.1-0.5 part by mass of curing accelerator, 15-85 parts by mass of inorganic filler and a proper amount of solvent at the temperature of 50-100 ℃ to uniformly mix to obtain a combined feed liquid (or called composite resin);
table 2: the specific raw material dosage (parts by mass, kg) of the combined feed liquid of the embodiments 2-1 to 2-8 is as follows:
the raw materials used in examples 2-1 to 2-8 were:
cyanate ester: bisphenol a cyanate ester, bisphenol F cyanate ester, yangzhou tianqi chemical ltd;
epoxy resin: o-cresol formaldehyde epoxy resin, the Shengquan group SQCN703, the epoxy equivalent of 200-210 g/eq, dicyclopentadiene phenol type epoxy resin, Jiashengde DPNE1501, the epoxy equivalent of 253 and 268 g/eq;
2-methylimidazole: forming four countries;
inorganic filler: silicon micropowder, Jiangsu biri NQ1040G, aluminum hydroxide, Yabao chemical company;
preparing a prepreg: and (3) placing the reinforcing material into the combined material liquid (fully) for soaking, taking out, and then baking at the temperature of 120-185 ℃ for 1-10 min to obtain the prepreg.
b. Preparing a laminate containing bismaleimide with a distorted non-planar configuration: attaching metal copper foils to two sides of the prepreg, cutting and superposing the prepreg according to the length, width and thickness requirements, placing the prepreg in a vacuum hot press, keeping the temperature rise rate of 1-3 ℃/min from room temperature to 100-180 ℃, keeping the prepreg pressed for 1-3 hours under the pressure of 0.3-1 MPa and the temperature of 100-180 ℃, then keeping the prepreg pressed for 1-3 hours, keeping the prepreg pressed for 180-250 ℃ under the temperature rise rate of 1-3 ℃/min, and pressing the prepreg for 1-5 hours under the pressure of 3-8 MPa and the temperature of 180-250 ℃ to obtain the twisted non-planar bismaleimide-containing laminated board (or called a damp-heat resistant laminated board).
Comparative example of the third section
Comparative examples 3-1 to 3-4: the bismaleimide is N, N-4, 4' -diphenylmethane bismaleimide (BDM for short), is modified with epoxy resin and allyl compounds, and then is prepared and added with curing agent hydrogen peroxide diisopropylbenzene, curing accelerator, inorganic filler and a proper amount of solvent to be uniformly mixed to obtain a combined feed liquid, so as to prepare the prepreg and the laminated board. The preparation processes of the combined feed liquid, the prepreg and the laminated board are the same, so that no difference is described.
Table 3: specific raw material amounts (parts by mass, kg) of the combined feed liquid of comparative examples 3-1 to 3-4:
comparative examples 3-1 to 3-4 used raw materials:
n, N-4, 4' -diphenylmethane bismaleimide: honghu Shuangma New materials Co., Ltd;
cyanate ester: bisphenol a cyanate ester, bisphenol F cyanate ester, yangzhou tianqi chemical ltd;
epoxy resin: o-cresol formaldehyde epoxy resin, the Shengquan group SQCN703, the epoxy equivalent of 200-210 g/eq, dicyclopentadiene phenol type epoxy resin, Jiashengde DPNE1501, the epoxy equivalent of 253 and 268 g/eq;
diallyl bisphenol A: laizhou Laiyu chemical Co., Ltd;
2-methylimidazole: forming four countries;
inorganic filler: silicon micropowder, Jiangsu biri NQ1040G, aluminum hydroxide, Yabao chemical company;
the composite resin prepared in the embodiment 2-1 to 2-4 without the third component has good solubility, and can be dissolved in a low-boiling point and low-toxicity solvent such as acetone, butanone, tetrahydrofuran, and the like. However, comparative examples 3-1 to 3-2, to which the third component was not added, were insoluble in acetone, methyl ethyl ketone, and tetrahydrofuran. The third component can be dissolved in a solvent such as acetone, butanone, tetrahydrofuran, etc. in examples 2-5 to 2-8 and comparative examples 3-3 to 3-4.
Table 4: solubility of composite resins of examples 2-1 to 2-8 and comparative examples 3-1 to 3-4:
note: in the table, "+ +" indicates dissolution at room temperature, "+ -" indicates dissolution by heating, and "-" indicates no dissolution.
As can be seen from Table 5 (including tables 5-1 and 5-2), the laminate obtained by applying the examples of the present invention has excellent heat resistance, low dielectric constant and dielectric loss, low moisture absorption rate and high peel strength. The distorted non-planar bismaleimide provided by the invention is suitable for the fields of heat resistance, moisture resistance and other composite material resin matrixes, electronic packaging materials and the like, and has a wide application prospect.
Table 5-1: examples 2-1 to 2-8 partial Performance parameters of the laminates:
tables 5-2: comparative examples 3-1 to 3-4 partial Performance parameters of the laminates:
the performance test methods in Table 5 (tables 5-1, 5-2) are as follows:
(1) glass transition temperature Tg:
the measurement was carried out according to the dynamic thermomechanical analysis (DMA) method defined by IPC-TM-650, 2.4.24.4.
(2) 5% Heat weight loss temperature (T)d5％)
The measurement was carried out according to the method defined in IPC-TM-650, 2.4.26.
(3) Dielectric constant Dk:
the dielectric constant data at 1GHz were measured by the plate method used in IPC-TM-650 at 2.5.5.9.
(4) Dielectric loss Df:
the dielectric loss data at 1GHz was measured according to the plate method used by 2.5.5.9 in IPC-TM-650.
(5) Moisture absorption rate:
measured according to the method defined in IPC-TM-650, 2.6.2.1.
(6) Peel strength:
the peel strength of the metal cap was measured according to the experimental conditions of "thermal stress" in the method specified in IPC-TM-650, 2.4.8.
Example 3:
a distorted non-planar bismaleimide having the general chemical structure shown in formula (I):
in formula (I): r1Halogen such as hydrogen, methyl, chlorine or bromine or an alkyl group having 1 to 8 carbon atoms; r2Is hydrogen or an alkyl group having 1 to 8 carbon atoms, and X is any one of-CO-O-, -S-, -O-or-CO-NH-.
Example 4:
a preparation method of bismaleimide with a distorted non-planar configuration comprises the following steps:
a. adding indane aromatic diamine into a reaction kettle, adding a proper amount of organic solvent, and stirring to dissolve the indane aromatic diamine;
b. dissolving maleic anhydride in a dosage ratio in an organic solvent, dropwise adding into a reaction kettle within 2h, and continuously stirring for 3h after dropwise adding is finished;
c. adding a certain amount of acetic anhydride and a catalyst, heating to 60 ℃, and carrying out heat preservation reaction for 5 hours;
d. and cooling after the reaction is finished, precipitating by using a large amount of water, filtering, and recrystallizing the obtained solid by using methylbenzene to obtain the bismaleimide with the distorted non-planar configuration.
Example 5:
a preparation method of bismaleimide with a distorted non-planar configuration comprises the following steps:
a. adding indane aromatic diamine into a reaction kettle, adding a proper amount of organic solvent, and stirring to dissolve the indane aromatic diamine;
b. dissolving maleic anhydride in a dosage ratio in an organic solvent, dropwise adding into a reaction kettle within 2.5h, and continuously stirring for 4h after dropwise adding is finished;
c. adding a certain amount of acetic anhydride and a catalyst, heating to 70 ℃, and carrying out heat preservation reaction for 4 hours;
d. and cooling after the reaction is finished, precipitating by using a large amount of water, filtering, and recrystallizing the obtained solid by using methylbenzene to obtain the bismaleimide with the distorted non-planar configuration.
Example 6:
a preparation method of bismaleimide with a distorted non-planar configuration comprises the following steps:
a. adding indane aromatic diamine into a reaction kettle, adding a proper amount of organic solvent, and stirring to dissolve the indane aromatic diamine;
b. dissolving maleic anhydride in a dosage ratio in an organic solvent, dropwise adding into a reaction kettle within 2.3h, and continuously stirring for 3.5h after dropwise adding is finished;
c. adding a certain amount of acetic anhydride and a catalyst, heating to 65 ℃, and carrying out heat preservation reaction for 4.5 hours;
d. and cooling after the reaction is finished, precipitating by using a large amount of water, filtering, and recrystallizing the obtained solid by using methylbenzene to obtain the bismaleimide with the distorted non-planar configuration.
Example 7:
a preparation method of bismaleimide with a distorted non-planar configuration is characterized by comprising the following steps:
a. adding 0.08mol of indane aromatic diamine into a reaction kettle, adding 100ml of organic solvent, and stirring to dissolve the indane aromatic diamine;
b. dissolving 0.20mol of maleic anhydride in 150ml of organic solvent, dropwise adding into the reaction kettle within 2h, and continuously stirring for 4h after dropwise adding is finished;
c. adding 0.22mol of acetic anhydride and 0.001mol of catalyst, heating to 60 ℃, and carrying out heat preservation reaction for 5 hours;
d. after the reaction is finished, cooling, precipitating by using (a large amount of) water, filtering, and recrystallizing the obtained solid by using methylbenzene to obtain the bismaleimide with the distorted non-planar configuration.
Example 8:
a preparation method of bismaleimide with a distorted non-planar configuration is characterized by comprising the following steps:
a. adding 0.08mol of indane aromatic diamine into a reaction kettle, adding 100ml of organic solvent, and stirring to dissolve the indane aromatic diamine;
b. dissolving 0.20mol of maleic anhydride in 150ml of organic solvent, dropwise adding into the reaction kettle within 2.5h, and continuously stirring for 3h after dropwise adding is finished;
c. adding 0.22mol of acetic anhydride and 0.001mol of catalyst, heating to 70 ℃, and reacting for 4 hours in a heat preservation way;
d. after the reaction is finished, cooling, precipitating by using (a large amount of) water, filtering, and recrystallizing the obtained solid by using methylbenzene to obtain the bismaleimide with the distorted non-planar configuration.
Example 9:
a preparation method of bismaleimide with a distorted non-planar configuration is characterized by comprising the following steps:
a. adding 0.08mol of indane aromatic diamine into a reaction kettle, adding 100ml of organic solvent, and stirring to dissolve the indane aromatic diamine;
b. dissolving 0.20mol of maleic anhydride in 150ml of organic solvent, dropwise adding into the reaction kettle within 2.2h, and continuously stirring for 3.5h after dropwise adding is finished;
c. adding 0.22mol of acetic anhydride and 0.001mol of catalyst, heating to 66 ℃, and reacting for 4.5 hours under the condition of heat preservation;
d. cooling (after the reaction is finished), precipitating by using (a large amount of) water, filtering, and recrystallizing the obtained solid by using toluene to obtain the bismaleimide with the distorted non-planar configuration.
In the above embodiments 4 to 9: the indane aromatic diamine in the step a can be any one or any combination of indane structure-containing aromatic diamine compounds containing isomers or substituted isomers; indane aromatic diamines are prepared as disclosed in US3856752 and US3983092, which are prior art.
The indane aromatic diamine may be specifically one or a mixture of two or more of 5(6) -amino-1- (4-aminophenyl) -1,3, 3-trimethylindane, 5(6) - (4-aminobenzamido) -1- (4-aminobenzamido) phenyl-1, 3, 3-trimethylindane, 5(6) - (4-aminophenoxy) -1- (4-aminophenoxy) phenyl-1, 3, 3-trimethylindane, and 5(6) - (4-aminobenzoyloxy) -1- (4-aminobenzoyloxy) phenyl-1, 3, 3-trimethylindane.
In the above embodiments 4 to 9: the organic solvent in the step a and the step b can be one or a mixture of more than two of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and acetone;
in the above embodiments 4 to 9: in the step c, the catalyst is one or a mixture of more than two of sodium acetate, nickel acetate, cobalt acetate and magnesium acetate.
Example 10:
a method for preparing a laminated board by using distorted non-planar configuration bismaleimide, comprising the following steps:
a. stirring (uniformly) 100 parts by mass of distorted non-planar bismaleimide and 10 parts by mass of cyanate at the temperature of 100 ℃, then adding 0.3 part by mass of hydrogen peroxide diisopropylbenzene, 0.1 part by mass of a curing accelerator, 15 parts by mass of an inorganic filler and a proper amount of a solvent at the temperature of 50 ℃, uniformly mixing to obtain a combined feed liquid, then placing a reinforcing material into the combined feed liquid for (fully) dipping, then taking out, and baking at the temperature of 120 ℃ for 10min to obtain a prepreg;
b. attaching metal copper foils on two sides of a prepreg, cutting and laminating according to the requirements of length, width and thickness, placing the prepreg in a vacuum hot press, keeping the temperature rise rate of 1 ℃/min from room temperature to 100 ℃, keeping the prepreg pressed for 3 hours under the pressure of 0.3MPa and the temperature of 100 ℃, then keeping the prepreg pressed for 3 hours under the pressure of 1 ℃/min, keeping the prepreg pressed for 180 ℃, and pressing the prepreg for 5 hours under the pressure of 3MPa and the temperature of 180 ℃ to obtain the laminated board (also called as a damp-heat resistant laminated board) containing the twisted non-planar bismaleimide.
Example 11:
a method for preparing a laminated board by using distorted non-planar configuration bismaleimide, comprising the following steps:
a. stirring (uniformly) 100 parts by mass of distorted non-planar bismaleimide and 100 parts by mass of cyanate at the temperature of 180 ℃, then adding 1.0 part by mass of hydrogen peroxide diisopropylbenzene, 0.5 part by mass of a curing accelerator, 85 parts by mass of an inorganic filler and a proper amount of a solvent at the temperature of 100 ℃, uniformly mixing to obtain a combined feed liquid, putting a reinforcing material into the combined feed liquid for (full) impregnation, taking out, and baking at the temperature of 185 ℃ for 1min to obtain a prepreg;
b. attaching metal copper foils to two sides of a prepreg, cutting and overlapping according to the requirements of length, width and thickness, placing the prepreg in a vacuum hot press, keeping the temperature rise rate of 3 ℃/min from room temperature to 180 ℃, keeping the prepreg pressed for 1h under the pressure of 1MPa and the temperature of 180 ℃, then keeping the prepreg pressed for 1h under the pressure of 3 ℃/min to 250 ℃, and pressing the prepreg for 1h under the pressure of 8MPa and the temperature of 1250 ℃ to obtain the laminated board (or called as a damp-heat resistant laminated board) containing the distorted non-planar bismaleimide.
Example 12:
a method for preparing a laminated board by using distorted non-planar configuration bismaleimide, comprising the following steps:
a. stirring (uniformly) 100 parts by mass of distorted non-planar bismaleimide and 55 parts by mass of cyanate at 140 ℃, then adding 0.7 part by mass of hydrogen peroxide diisopropylbenzene, 0.3 part by mass of a curing accelerator, 50 parts by mass of an inorganic filler and a proper amount of a solvent at 75 ℃ and uniformly mixing to obtain a combined feed liquid, then placing a reinforcing material into the combined feed liquid (fully) for dipping and then taking out, and baking at 155 ℃ for 5min to obtain a prepreg;
b. attaching metal copper foils to two sides of a prepreg, cutting and laminating according to the requirements of length, width and thickness, placing the prepreg in a vacuum hot press, keeping the temperature rise rate of 2 ℃/min from room temperature to 140 ℃, keeping the prepreg pressed for 2h under the pressure of 0.7MPa and the temperature of 140 ℃, then keeping the prepreg pressed for 2h, keeping the prepreg pressed for 220 ℃ under the temperature rise rate of 2 ℃/min, and pressing the prepreg for 3h under the pressure of 6MPa and the temperature of 220 ℃ to obtain the laminated board (also called as a damp-heat resistant laminated board) containing the distorted non-planar bismaleimide.
Example 13:
a method for preparing a laminated board by using distorted non-planar configuration bismaleimide, comprising the following steps:
a. stirring (uniformly) 100 parts by mass of distorted non-planar bismaleimide, 10 parts by mass of cyanate ester, 20 parts by mass of epoxy resin and 5 parts by mass of allyl phenolic compound at the temperature of 100 ℃, then adding 0.3 part by mass of hydrogen peroxide diisopropylbenzene, 0.1 part by mass of curing accelerator, 15 parts by mass of inorganic filler and a proper amount of solvent at the temperature of 50 ℃, uniformly mixing to obtain a combined feed liquid, putting the reinforcing material into the combined feed liquid for (full) dipping, taking out, and baking at the temperature of 120 ℃ for 1min to obtain a prepreg;
b. attaching metal copper foils on two sides of a prepreg, cutting and laminating according to the requirements of length, width and thickness, placing the prepreg in a vacuum hot press, keeping the temperature rise rate of 1 ℃/min from room temperature to 100 ℃, keeping the prepreg pressed for 1h under the pressure of 0.3MPa and the temperature of 100 ℃, then keeping the prepreg pressed for 1h under the pressure of 1 ℃/min to 180 ℃, and pressing the prepreg for 1h under the pressure of 3MPa and the temperature of 180 ℃ to obtain the laminated board (also called as a damp-heat resistant laminated board) containing the distorted non-planar bismaleimide.
Example 14:
a method for preparing a laminated board by using distorted non-planar configuration bismaleimide, comprising the following steps:
a. stirring (uniformly) 100 parts by mass of distorted non-planar bismaleimide, 100 parts by mass of cyanate ester, 40 parts by mass of epoxy resin and 20 parts by mass of allyl phenolic compound at the temperature of 180 ℃, then adding 1.0 part by mass of diisopropylbenzene hydroperoxide, 0.5 part by mass of curing accelerator, 85 parts by mass of inorganic filler and a proper amount of solvent at the temperature of 100 ℃ and uniformly mixing to obtain a combined feed liquid, putting the reinforcing material into the combined feed liquid for (full) dipping and then taking out, and baking at the temperature of 185 ℃ for 10min to obtain a prepreg;
b. attaching metal copper foils on two sides of a prepreg, cutting and overlapping according to the requirements of length, width and thickness, placing the prepreg in a vacuum hot press, keeping the temperature rise rate of 3 ℃/min from room temperature to 180 ℃, keeping the prepreg pressed for 3 hours under the pressure of 1MPa and the temperature of 180 ℃, then keeping the prepreg pressed for 3 hours under the pressure of 3 ℃/min to 250 ℃, and pressing the prepreg for 5 hours under the pressure of 8MPa and the temperature of 250 ℃ to obtain the laminated board (or called as a damp-heat resistant laminated board) containing the distorted non-planar bismaleimide.
Example 15:
a method for preparing a laminated board by using distorted non-planar configuration bismaleimide, comprising the following steps:
a. stirring (uniformly) 100 parts by mass of distorted non-planar bismaleimide, 55 parts by mass of cyanate ester, 30 parts by mass of epoxy resin and 23 parts by mass of allyl phenolic compound at the temperature of 140 ℃, then adding 0.65 part by mass of diisopropylbenzene hydroperoxide, 0.3 part by mass of curing accelerator, 50 parts by mass of inorganic filler and a proper amount of solvent at the temperature of 77 ℃, uniformly mixing to obtain a combined feed liquid, putting the reinforcing material into the combined feed liquid for (full) dipping, taking out, and baking at the temperature of 152 ℃ for 6min to obtain a prepreg;
b. attaching metal copper foils to two sides of a prepreg, cutting and overlapping according to the requirements of length, width and thickness, placing the prepreg in a vacuum hot press, keeping the temperature rise rate of 2 ℃/min from room temperature to 140 ℃, keeping the prepreg pressed for 2h under the pressure of 0.6MPa and the temperature of 140 ℃, then keeping the prepreg pressed for 2h, keeping the prepreg pressed for 215 ℃ under the temperature rise rate of 2 ℃/min, and pressing the prepreg for 3h under the pressure of 5.5MPa and the temperature of 215 ℃ to obtain the laminated board (or called as a damp-heat resistant laminated board) containing the distorted non-planar bismaleimide.
Example 16:
a method for preparing a laminated board by using distorted non-planar configuration bismaleimide, comprising the following steps:
a. stirring (uniformly) 100 parts by mass of distorted non-planar bismaleimide, 35 parts by mass of cyanate ester, 28 parts by mass of epoxy resin and 8 parts by mass of allyl phenolic compound at 120 ℃, then adding 0.5 part by mass of diisopropylbenzene hydroperoxide, 0.2 part by mass of curing accelerator, 35 parts by mass of inorganic filler and a proper amount of solvent at 65 ℃ and uniformly mixing to obtain a combined feed liquid, putting the reinforcing material into the combined feed liquid for (fully) soaking, then taking out, and baking at 130 ℃ for 7min to obtain a prepreg;
b. attaching metal copper foils to two sides of a prepreg, cutting and laminating according to the requirements of length, width and thickness, placing the prepreg in a vacuum hot press, keeping the temperature rise rate of 2 ℃/min from room temperature to 120 ℃, keeping the prepreg pressed for 2h under the pressure of 0.5MPa and the temperature of 120 ℃, then keeping the prepreg pressed for 2h under the pressure of 2 ℃/min to 195 ℃, and pressing the prepreg for 4h under the pressure of 4MPa and the temperature of 195 ℃ to obtain the laminated board (also called as a damp-heat resistant laminated board) containing the distorted non-planar bismaleimide.
In the above embodiments 10 to 15:
the distorted non-planar configuration bismaleimide in the step a is obtained by the preparation;
the cyanate is any one of bisphenol A cyanate, bisphenol M cyanate, bisphenol F cyanate, tetramethyl bisphenol F cyanate, phenolic cyanate and cyclopentadiene cyanate;
the epoxy resin is one or a mixture of more than two of bisphenol A type epoxy resin (such as Shengquan SQP-40AXM40, great alignment DYD-115 and baring petrochemical E-44), phenolic epoxy resin (such as Shengquan SQPN-051, great alignment PGCN-701 and baring petrochemical CYDCN-200);
the allyl phenolic compound is any one of diallyl bisphenol A, allyl phenol and 2, 2' -diallyl bisphenol A;
the curing accelerator is any one of imidazole compounds (such as 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole formed by four countries) and acetylacetone transition metal complexes (such as cobalt acetylacetonate, zinc acetylacetonate and chromium acetylacetonate);
the inorganic filler is one or a mixture of more than two of magnesium hydroxide, calcium carbonate, aluminum hydroxide, silicon dioxide, silicon micropowder, hollow glass beads and gas-phase silicon dioxide;
the solvent is one or a mixture of more than two of butanone, toluene, xylene, acetone, propylene glycol monomethyl ether and N, N-dimethylformamide.
In the above embodiments 10 to 15: the reinforcing material in the step a is any one of organic synthetic fiber, organic fabric, natural fiber and inorganic fabric.
In the above embodiments 10 to 15: the thickness of the metal copper foil in the step b is not limited.
In the above embodiment: the percentages used, not specifically indicated, are mass (weight) ratios or percentages known to those skilled in the art; the parts by mass (by weight) may all be grams or kilograms.
In the above embodiment: the process parameters (temperature, time, 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.