Allyl compound, preparation method of allyl compound, bismaleimide resin composition and application of bismaleimide resin composition

Abstract

The invention relates to the technical field of semiconductors, in particular to an allyl compound, a preparation method of the allyl compound, a bismaleimide resin composition and application of the bismaleimide resin composition. The allyl compound has a structure as shown in a formula I. After the compound with the structure reacts with bismaleimide resin, a larger loose structure can be formed in the bismaleimide material, so that the internal free volume of the material is increased, and the dielectric constant and dielectric loss of the bismaleimide material can be greatly reduced; and the bismaleimide material can be used as a low-dielectric packaging carrier plate material to be applied to the field of high-frequency and high-speed communication. And the formula I of the # imgabs0 # is shown in the specification.

Description

Technical Field

[0001] The present application relates to the field of semiconductor technology, and in particular to an allyl compound and a preparation method thereof, a bismaleimide resin composition and an application thereof. Background Art

[0002] In the era of high frequency and high speed, low dielectric materials are currently a hot research direction. Among them, low dielectric packaging substrate materials have high performance requirements and are difficult to develop. Currently, this material is mainly controlled by a few foreign giants. It can be seen that the development of low dielectric packaging substrate materials is of great strategic significance to the development of my country's semiconductor packaging field.

[0003] Bismaleimide is a material that plays an important role in the field of semiconductor packaging, especially as one of the key raw materials for packaging substrates. Its special imide ring ensures that the material has excellent heat resistance and dimensional stability. However, bismaleimide is brittle and has low solubility. In order to solve the problems of high brittleness and low solubility, it has been reported that DABPA, DABPS, DDS, DDM, etc. are used to extend the chain of bismaleimide resin, but the dielectric loss of the prepared materials is relatively large, which limits the application of bismaleimide in high-frequency and high-speed fields. Summary of the invention

[0004] Based on this, the first aspect of the present application provides an allyl compound, and its technical solution is as follows:

[0005] An allyl compound having a structure shown in Formula I:

[0006] Formula I;

[0007] Wherein, L is selected from a single bond, -CH2-, -S(=O)(=O)- or -C(CH3)(CH3)-; and R is selected from a fluorine-substituted C1-C8 alkyl group.

[0008] The second aspect of the present application provides a method for preparing an allyl compound, and its technical scheme is as follows:

[0009] A method for preparing an allyl compound comprises the following steps:

[0010] Mixing a compound of formula II, a compound of formula III, an acid-binding agent and a solvent to react and generate a compound of formula II;

[0011] Formula II; Formula III;

[0012] Formula I;

[0013] Wherein, L is selected from a single bond, -CH2-, -S(=O)(=O)- or -C(CH3)(CH3)-; and R is selected from a fluorine-substituted C1-C8 alkyl group.

[0014] The third aspect of the present application provides a bismaleimide resin composition, and its technical solution is as follows:

[0015] A bismaleimide resin composition comprises a bismaleimide resin and the allyl compound mentioned above.

[0016] The fourth aspect of the present application provides a prepolymer glue solution, the raw materials of which include the bismaleimide resin composition as described above.

[0017] The fifth aspect of the present application provides a method for preparing a prepolymer glue solution, and the technical solution thereof is as follows:

[0018] A method for preparing a prepolymer glue solution comprises the following steps:

[0019] The bismaleimide resin and the allyl compound are polymerized.

[0020] A sixth aspect of the present application provides a prepreg, the raw materials of which include a reinforcing material and the prepolymer glue as described above.

[0021] A seventh aspect of the present application provides a laminate, the raw materials of which include a metal foil and the prepreg as described above, or include a metal foil and the prepolymer glue as described above.

[0022] Compared with the traditional solution, this application has the following beneficial effects:

[0023] The allyl compounds provided in the present application contain fluorine atoms, which have strong electron-withdrawing ability, making it difficult for the carbon-fluorine bond to be polarized. At the same time, the strong repulsion between fluorine atoms will hinder the stacking of chain segments. After the compound with the above structure reacts with the bismaleimide resin, a larger loose structure will be formed inside the bismaleimide material, increasing the free volume inside the material, which can greatly reduce the dielectric constant and dielectric loss of the bismaleimide material, so that the bismaleimide material can be used as a low-dielectric packaging substrate material in the field of high-frequency and high-speed communications. DETAILED DESCRIPTION

[0024] The present application will be further described in detail below in conjunction with specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thoroughly understood.

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0026] the term

[0027] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0028] In this application, "optionally", "optional" and "optional" refer to optional, that is, to any one of the two parallel schemes of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0029] In this application, in the "first aspect", "second aspect", "third aspect", "fourth aspect", etc., the terms "first", "second", "third", "fourth", etc. are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0030] In the present application, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the optional numerical distribution within the above numerical interval is deemed to be continuous and includes the two numerical endpoints of the numerical range (i.e., the minimum value and the maximum value), and every numerical value between the two numerical endpoints.

[0031] The temperature parameters in this application, unless otherwise specified, are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within the range of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.

[0032] The first aspect of the present application provides an allyl compound, and the technical solution thereof is as follows:

[0033] An allyl compound having a structure shown in Formula I:

[0034] Formula I;

[0035] Wherein, L is selected from a single bond, -CH2-, -S(=O)(=O)- or -C(CH3)(CH3)-; and R is selected from a fluorine-substituted C1-C8 alkyl group.

[0036] The above-mentioned allyl compounds contain fluorine atoms, which have strong electron-withdrawing ability, making it difficult for the carbon-fluorine bond to be polarized. At the same time, the strong repulsion between fluorine atoms will hinder the stacking of chain segments. After the compound with the above structure reacts with the bismaleimide resin, a larger loose structure will be formed inside the bismaleimide material, increasing the free volume inside the material, which can greatly reduce the dielectric constant and dielectric loss of the bismaleimide material, so that the bismaleimide material can be used as a low-dielectric packaging substrate material in the field of high-frequency and high-speed communications.

[0037] Optionally, the allyl compound has a structure shown in any one of formula (I-1) to formula (I-2):

[0038] Formula (I-1)

[0039] Formula (I-2).

[0040] Optionally, R is selected from a perfluorinated C1-C8 alkyl group. For example, R is selected from a perfluorinated methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl group. As the number of carbon atoms in the alkyl chain increases, the more fluorine atoms there are.

[0041] The second aspect of the present application provides a method for preparing an allyl compound, and its technical scheme is as follows:

[0042] A method for preparing an allyl compound comprises the following steps:

[0043] Mixing a compound of formula II, a compound of formula III, an acid-binding agent and a solvent to react and generate a compound of formula II;

[0044] Formula II; Formula III;

[0045] Formula I;

[0046] Among them, L and R are as described above and will not be repeated here.

[0047] The above preparation method removes the high polar hydroxyl group by reacting the fluorine-containing acyl chloride with the hydroxyl group of the compound of formula II, and introduces fluorine atoms at the same time. The fluorine atoms have strong electron-withdrawing ability, making the carbon-fluorine bond difficult to be polarized, and the strong repulsion between the fluorine atoms will hinder the stacking between the segments. After the prepared allyl compound is reacted with the bismaleimide resin, a larger loose structure is formed inside the maleimide material, which increases the internal free volume of the material, can greatly reduce the dielectric constant and dielectric loss of the dual material, so that the bismaleimide material can be used as a low dielectric packaging substrate material in the field of high-frequency and high-speed communications.

[0048] Optionally, the compound of formula II is selected from at least one of 3,3'-diallyl bisphenol S, 2,2'-diallyl bisphenol A and magnolol. Among them, the structural formula of 3,3'-diallyl bisphenol S is: The structural formula of 2,2'-diallyl bisphenol A is: The structural formula of magnolol is: .

[0049] Optionally, the compound of formula III is selected from at least one of trifluoroacetyl chloride, pentafluoropropionyl chloride, heptafluorobutyryl chloride, nonafluoropentanoyl chloride, undecafluorohexanoyl chloride, tridecafluoroheptanoyl chloride, pentafluorooctanoyl chloride and heptadecafluorononanoyl chloride.

[0050] Optionally, the molar ratio of the compound of formula II to the compound of formula III is 1:(1.5-2.5). For example, the molar ratio is 1:1.5, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.5.

[0051] Optionally, the acid binding agent includes at least one of potassium carbonate, sodium carbonate and triethylamine.

[0052] Optionally, the mass of the acid binding agent accounts for 20% to 60% of the total mass of the compound of formula II and the compound of formula III, for example, 20%, 30%, 40%, or 50% of the total mass.

[0053] In some embodiments, among the above raw materials, the weight portion of the compound of formula II is 60 to 150 parts, the weight portion of the compound of formula III is 71 to 346 parts, and the weight portion of the acid binding agent is 37 to 125 parts.

[0054] Optionally, the solvent comprises chloroform.

[0055] Optionally, the reaction temperature is -10°C to 10°C. For example, the reaction temperature is -10°C, -5°C, -2°C, 0°C, 2°C, 5°C, 10°C.

[0056] Optionally, the reaction time is 4 h to 8 h. For example, the reaction time is 4 h, 5 h, 6 h, 7 h, or 8 h.

[0057] The raw materials used in the above preparation method have all been industrialized, are cheap and easily available, and the chemical synthesis reaction is simple, with fewer steps, and is easy to industrialize and applicable to existing production lines.

[0058] The third aspect of the present application provides a bismaleimide resin composition, and its technical solution is as follows:

[0059] A bismaleimide resin composition comprises a bismaleimide resin and the allyl compound mentioned above.

[0060] In the above-mentioned bismaleimide resin composition, the allyl compound can further undergo an ene reaction with the bismaleimide resin to obtain a linear prepolymer. The linear prepolymer is generated by the ene reaction, which greatly reduces the dielectric properties of the bismaleimide material while ensuring the processability and solves the problems of low solubility and poor toughness of the bismaleimide resin.

[0061] Optionally, the weight portion of the bismaleimide resin is 100-240 parts; the weight portion of the allyl compound is 60-220 parts.

[0062] Optionally, the bismaleimide resin includes at least one of N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N'-m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 1,1-(4-methyl-1,3-phenylene)bis-1H-pyrrole-2,5-dione and 1,1'-(2,2,4-trimethyl-1,6-hexanediyl)bis-1H-pyrrole-2,5-dione.

[0063] Optionally, the bismaleimide resin composition further comprises a flame retardant containing an acrylic group, a filler and a solvent.

[0064] Optionally, the weight of the bismaleimide resin is 100-240 parts; the weight of the allyl compound is 60-220 parts; the weight of the acryl-containing flame retardant is 4-12 parts; the weight of the filler is 246-708 parts and the weight of the solvent is 330-910 parts.

[0065] Optionally, the acryl-containing flame retardant includes at least one of diethyl allyl phosphate, dimethyl allyl phosphate, diisopropyl allyl phosphate, triallyl phosphate and diethyl (2-methylallyl) phosphonate.

[0066] Optionally, the filler comprises silica microspheres with surface grafted acrylate.

[0067] Optionally, the solvent includes at least one of toluene, cyclohexanone, butanone and acetone.

[0068] The fourth aspect of the present application provides a prepolymer glue solution, the raw materials of which include the bismaleimide resin composition as described above.

[0069] The fifth aspect of the present application provides a method for preparing a prepolymer glue solution, and the technical solution thereof is as follows:

[0070] A method for preparing a prepolymer glue solution comprises the following steps:

[0071] The bismaleimide resin and the allyl compound are polymerized.

[0072] Allyl compounds react with bismaleimide resin to obtain linear prepolymers. Compared with simple blending, the prepolymer chain is extended by prepolymerization. While the dielectric properties of the bismaleimide material are greatly reduced, the processability can be guaranteed and the problems of low solubility and poor toughness of the bismaleimide resin are solved.

[0073] Optionally, the bismaleimide resin composition further comprises a flame retardant containing an propylene group, a filler and a solvent, and the bismaleimide resin and the allyl compound are polymerized, comprising the following steps:

[0074] The bismaleimide resin, the allyl compound, the acryl-containing flame retardant and the solvent are mixed to cause a polymerization reaction, and then the filler is added.

[0075] The above polymerization reaction does not require purification, the operation is simple, a large amount of solvent is saved, and industrial production is easy to achieve.

[0076] Optionally, the polymerization reaction comprises the following procedure: reacting at 120° C. to 140° C. for 1 h to 3 h, then heating to 150° C. to 170° C. and continuing to react for 1 h to 3 h.

[0077] Optionally, after adding the filler, stir for 1 h to 3 h.

[0078] A sixth aspect of the present application provides a prepreg, the raw materials of which include a reinforcing material and the prepolymer glue as described above.

[0079] Alternatively, the reinforcement material may be fiberglass cloth.

[0080] The above-mentioned prepreg can be prepared by impregnating the reinforcing material into a prepolymer glue solution.

[0081] A seventh aspect of the present application provides a laminate, the raw materials of which include a metal foil and the prepreg as described above, or include a metal foil and the prepolymer glue as described above.

[0082] The allyl compounds provided in the present application are used for pre-polymerization and chain extension with bismaleimide resin, which improves the solubility and toughness of the bismaleimide material while reducing the dielectric constant and loss of the bismaleimide material, and can meet the stringent requirements of high-frequency and high-speed fields for packaging carrier materials.

[0083] The following is further described in conjunction with specific embodiments and comparative examples. The raw materials involved in the following specific embodiments and comparative examples, unless otherwise specified, can all be commercially available, the instruments used, unless otherwise specified, can all be commercially available, and the processes involved, unless otherwise specified, are all routinely selected by those skilled in the art.

[0084] Among them, 3,3'-diallylbisphenol S was purchased from Beijing Huawei Ruike Chemical Technology Co., Ltd., 2,2'-diallylbisphenol A and magnolol were purchased from Anhui Zesheng Technology Co., Ltd., N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N'-m-phenylenebismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 1,1-(4-methyl-1,3-phenylene)bis-1H-pyrrole-2,5-dione and 1,1'-(2,2,4-trimethyl-1,6-hexanediyl)bis-1H-pyrrole-2,5-dione were purchased from Yamato Chemical Co., Ltd. of Japan. Allyl diethyl phosphate, allyl dimethyl phosphate, allyl diisopropyl phosphate, triallyl phosphate and diethyl (2-methylallyl) phosphonate were purchased from Anhui Zesheng Technology Co., Ltd.

[0085] Example 1

[0086] This embodiment provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, and the steps are as follows:

[0087] 1. Preparation of allyl compounds

[0088] 150g 3,3'-diallylbisphenol S (about 0.45mol) and 125g potassium carbonate were added to a three-necked flask containing 800g chloroform in sequence, placed in an ice bath (0°C) and continuously stirred and nitrogen was passed through, and then 121g trifluoroacetyl chloride (about 0.9mol) was added dropwise through a constant pressure dropping funnel. After reacting for 6 hours, the temperature was raised to room temperature, the residue was removed by filtration, the filtrate was washed 6 times with deionized water, and the water layer was removed by a separatory funnel to retain the organic layer, and the solvent was further removed by rotary evaporation to obtain an allyl compound.

[0089] 2. Preparation of prepolymer glue

[0090] 150g of the above-mentioned allyl compound, 220g of N,N'-(4,4'-methylenediphenyl)bismaleimide, 10g of diethyl allyl phosphate, 200g of toluene, 200g of cyclohexanone and 330g of butanone were added to a three-necked flask in sequence, heated to 130°C for reaction for 2 hours under continuous nitrogen flow and stirring, then further heated to 160°C for continued reaction for 2 hours, cooled to room temperature, added 570g of surface-grafted acrylate silica microspheres, and continued stirring for 2 hours to obtain a prepolymer glue solution.

[0091] 3. Preparation of prepreg and laminate

[0092] 2116 glass fiber cloth (basic weight 105g / m 2 ) was immersed in the above-mentioned prepolymer glue solution, taken out and placed in an oven at 185°C for 4 minutes to obtain a prepreg with a glue content of 50wt%. 8 prepregs were stacked and covered with 18-micron electrolytic copper foil, placed in a vacuum press, and the pressure was set to 28kgf / cm 2 , pressed at 200°C for 2 hours, then heated to 220°C and continued pressed for 1 hour, and finally cooled and taken out to prepare a laminate with a thickness of 0.85 mm.

[0093] Example 2

[0094] This embodiment provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, and the steps are as follows:

[0095] 1. Preparation of allyl compounds

[0096] 100 g of 2,2'-diallyl bisphenol A (about 0.325 mol) and 69 g of sodium carbonate were added successively into a three-necked flask containing 650 g of chloroform, placed in an ice bath (0°C) and continuously stirred and nitrogen was passed through, and then 119 g of pentafluoropropionyl chloride (about 0.65 mol) was added dropwise through a constant pressure dropping funnel. After reacting for 6 hours, the temperature was raised to room temperature, the residue was removed by filtration, the filtrate was washed 6 times with deionized water, the water layer was removed by a separatory funnel and the organic layer was retained, and then the solvent was further removed by rotary evaporation to obtain an allyl compound.

[0097] 2. Preparation of prepolymer glue

[0098] 100g of the above-mentioned allyl compound, 160g of N,N'-m-phenylene bismaleimide, 8g of allyl dimethyl phosphate, 150g of toluene, 150g of cyclohexanone and 220g of butanone were added into a three-necked flask in sequence, heated to 130°C for reaction for 2 hours under continuous nitrogen flow and stirring, then further heated to 160°C for continued reaction for 2 hours, cooled to room temperature, added 402g of surface-grafted acrylate silica microspheres, and continued stirring for 2 hours to obtain a prepolymer glue solution.

[0099] 3. Preparation of prepreg and laminate

[0100] Same as Example 1.

[0101] Example 3

[0102] This embodiment provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, and the steps are as follows:

[0103] 1. Preparation of allyl compounds

[0104] 60 g of magnolol (about 0.225 mol) and 46 g of triethylamine were added in sequence to a three-necked flask containing 500 g of chloroform, placed in an ice bath (0°C) and continuously stirred and nitrogen was passed through, and then 105 g of heptafluorobutyryl chloride (about 0.45 mol) was added dropwise through a constant pressure dropping funnel. After reacting for 6 hours, the temperature was raised to room temperature, and the residue was removed by filtration. The filtrate was washed 6 times with deionized water, and the water layer was removed by a separatory funnel to retain the organic layer, and the solvent was further removed by rotary evaporation to obtain an allyl compound.

[0105] 2. Preparation of prepolymer glue

[0106] 80g of the above-mentioned allyl compound, 120g of 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 6g of diisopropyl allyl phosphate, 120g of toluene, 120g of cyclohexanone and 160g of butanone were added into a three-necked flask in sequence, heated to 130°C for reaction for 2 hours under continuous nitrogen flow and stirring, then further heated to 160°C for continued reaction for 2 hours, cooled to room temperature, added with 309g of surface-grafted acrylate silica microspheres, and continued stirring for 2 hours to obtain a prepolymer glue solution.

[0107] 3. Preparation of prepreg and laminate

[0108] Same as Example 1.

[0109] Example 4

[0110] This embodiment provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, and the steps are as follows:

[0111] 1. Preparation of allyl compounds

[0112] 90 g of honokiol (about 0.34 mol) and 68 g of triethylamine were added in sequence to a three-necked flask containing 850 g of chloroform, placed in an ice bath (0°C) and continuously stirred and nitrogen was passed through, and then 192 g of nonafluorovaleryl chloride (about 0.68 mol) was added dropwise through a constant pressure dropping funnel. After reacting for 6 hours, the temperature was raised to room temperature, the residue was removed by filtration, the filtrate was washed 6 times with deionized water, and the water layer was removed by a separatory funnel to retain the organic layer, and the solvent was further removed by rotary evaporation to obtain an allyl compound.

[0113] 2. Preparation of prepolymer glue

[0114] 120g of the above-mentioned allyl compound, 160g of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 8g of triallyl phosphate, 160g of toluene, 160g of cyclohexanone and 340g of butanone were added into a three-necked flask in sequence, heated to 130°C for reaction for 2 hours under continuous nitrogen flow and stirring, then further heated to 160°C for continued reaction for 2 hours, cooled to room temperature, added 432g of surface-grafted acrylate silica microspheres, and continued stirring for 2 hours to obtain a prepolymer glue solution.

[0115] 3. Preparation of prepreg and laminate

[0116] Same as Example 1.

[0117] Example 5

[0118] This embodiment provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, and the steps are as follows:

[0119] 1. Preparation of allyl compounds

[0120] 80 g of magnolol (about 0.3 mol) and 65 g of sodium carbonate were added in sequence to a three-necked flask containing 850 g of chloroform, placed in an ice bath (0°C) and continuously stirred and nitrogen was passed through, and then 200 g of undecanoyl chloride (about 0.6 mol) was added dropwise through a constant pressure dropping funnel. After reacting for 6 hours, the temperature was raised to room temperature, and the residue was removed by filtration. The filtrate was washed 6 times with deionized water, and the water layer was removed by a separatory funnel to retain the organic layer, and the solvent was further removed by rotary evaporation to obtain an allyl compound.

[0121] 2. Preparation of prepolymer glue

[0122] 100g of the above-mentioned allyl compound, 140g of 1,1-(4-methyl-1,3-phenylene)di-1H-pyrrole-2,5-dione, 6g of diethyl (2-methylallyl)phosphonate, 140g of toluene, 140g of cyclohexanone and 200g of butanone were added into a three-necked flask in sequence, heated to 130°C for reaction for 2 hours under continuous nitrogen flow and stirring, then further heated to 160°C for continued reaction for 2 hours, cooled to room temperature, added 369g of surface-grafted acrylate silica microspheres, and continued stirring for 2 hours to obtain a prepolymer glue solution.

[0123] 3. Preparation of prepreg and laminate

[0124] Same as Example 1.

[0125] Example 6

[0126] This embodiment provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, and the steps are as follows:

[0127] 1. Preparation of allyl compounds

[0128] 120 g of magnolol (about 0.45 mol) and 125 g of potassium carbonate were added in sequence to a three-necked flask containing 1400 g of chloroform, placed in an ice bath (0°C) and continuously stirred and nitrogen was passed through, and then 346 g of tridecafluoroheptanoyl chloride (about 0.9 mol) was added dropwise through a constant pressure dropping funnel. After reacting for 6 hours, the temperature was raised to room temperature, the residue was removed by filtration, the filtrate was washed 6 times with deionized water, and the water layer was removed by a separatory funnel to retain the organic layer, and the solvent was further removed by rotary evaporation to obtain an allyl compound.

[0129] 2. Preparation of prepolymer glue

[0130] 200g of the above-mentioned allyl compound, 220g of 1,1'-(2,2,4-trimethyl-1,6-hexanediyl)bis-1H-pyrrole-2,5-dione, 10g of diethyl (2-methylallyl)phosphonate, 220g of toluene, 220g of cyclohexanone and 390g of butanone were added into a three-necked flask in sequence, heated to 130°C for reaction for 2 hours under continuous nitrogen flow and stirring, then further heated to 160°C for continued reaction for 2 hours, cooled to room temperature, added 645g of surface-grafted acrylate silica microspheres, and continued stirring for 2 hours to obtain a prepolymer glue solution.

[0131] 3. Preparation of prepreg and laminate

[0132] Same as Example 1.

[0133] Example 7

[0134] This embodiment provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, and the steps are as follows:

[0135] 1. Preparation of allyl compounds

[0136] 150 g of 2,2'-diallyl bisphenol A (about 0.485 mol) and 134 g of potassium carbonate were added to a three-necked flask containing 1400 g of chloroform in sequence, placed in an ice bath (0°C) and continuously stirred and nitrogen was passed through, and then 324 g of undecanoyl chloride (about 0.97 mol) was added dropwise through a constant pressure dropping funnel. After reacting for 6 hours, the temperature was raised to room temperature, the residue was removed by filtration, the filtrate was washed 6 times with deionized water, and the water layer was removed by a separatory funnel to retain the organic layer, and the solvent was further removed by rotary evaporation to obtain an allyl compound.

[0137] 2. Preparation of prepolymer glue

[0138] 220g of the above-mentioned allyl compound, 240g of 1,1'-(2,2,4-trimethyl-1,6-hexanediyl)bis-1H-pyrrole-2,5-dione, 12g of triallyl phosphate, 250g of toluene, 250g of cyclohexanone and 410g of butanone were added into a three-necked flask in sequence, heated to 130°C for reaction for 2 hours under continuous nitrogen flow and stirring, then further heated to 160°C for continued reaction for 2 hours, cooled to room temperature, added 708g of surface-grafted acrylate silica microspheres, and continued stirring for 2 hours to obtain a prepolymer glue solution.

[0139] 3. Preparation of prepreg and laminate

[0140] Same as Example 1.

[0141] Example 8

[0142] This embodiment provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, and the steps are as follows:

[0143] 1. Preparation of allyl compounds

[0144] 100 g of 3,3'-diallylbisphenol S (about 0.3 mol) and 64 g of sodium carbonate were added to a three-necked flask containing 800 g of chloroform in sequence, placed in an ice bath (0°C) and continuously stirred and nitrogen was passed through, and then 172 g of nonafluorovaleryl chloride (about 0.6 mol) was added dropwise through a constant pressure dropping funnel. After reacting for 6 hours, the temperature was raised to room temperature, the residue was removed by filtration, the filtrate was washed 6 times with deionized water, and the water layer was removed by a separatory funnel to retain the organic layer, and the solvent was further removed by rotary evaporation to obtain an allyl compound.

[0145] 2. Preparation of prepolymer glue

[0146] 130g of the above-mentioned allyl compound, 140g of 1,1-(4-methyl-1,3-phenylene)di-1H-pyrrole-2,5-dione, 6g of diisopropyl allyl phosphate, 160g of toluene, 160g of cyclohexanone and 220g of butanone were added into a three-necked flask in sequence, heated to 130°C for reaction for 2 hours under continuous nitrogen flow and stirring, then further heated to 160°C for continued reaction for 2 hours, cooled to room temperature, added 414g of surface-grafted acrylate silica microspheres, and continued stirring for 2 hours to obtain a prepolymer glue solution.

[0147] 3. Preparation of prepreg and laminate

[0148] Same as Example 1.

[0149] Example 9

[0150] This embodiment provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, and the steps are as follows:

[0151] 1. Preparation of allyl compounds

[0152] 60 g of 3,3'-diallylbisphenol S (about 0.18 mol) and 37 g of triethylamine were added to a three-necked flask containing 450 g of chloroform in sequence, placed in an ice bath (0°C) and continuously stirred and nitrogen was passed through, and then 85 g of heptafluorobutyryl chloride (about 0.36 mol) was added dropwise through a constant pressure dropping funnel. After reacting for 6 hours, the temperature was raised to room temperature, the residue was removed by filtration, the filtrate was washed 6 times with deionized water, and the water layer was removed by a separatory funnel to retain the organic layer, and the solvent was further removed by rotary evaporation to obtain an allyl compound.

[0153] 2. Preparation of prepolymer glue

[0154] 60g of the above-mentioned allyl compound, 100g of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 4g of allyl dimethyl phosphate, 90g of toluene, 90g of cyclohexanone and 150g of butanone were added into a three-necked flask in sequence, heated to 130°C for reaction for 2 hours under continuous nitrogen flow and stirring, then further heated to 160°C for continued reaction for 2 hours, cooled to room temperature, added with 246g of surface-grafted acrylate silica microspheres, and continued stirring for 2 hours to obtain a prepolymer glue solution.

[0155] 3. Preparation of prepreg and laminate

[0156] Same as Example 1.

[0157] Example 10

[0158] This embodiment provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, and the steps are as follows:

[0159] 1. Preparation of allyl compounds

[0160] 60 g of 2,2'-diallyl bisphenol A (about 0.195 mol) and 39 g of triethylamine were added to a three-necked flask containing 400 g of chloroform in sequence, placed in an ice bath (0°C) and continuously stirred and nitrogen was passed through, and then 71 g of pentafluoropropionyl chloride (about 0.39 mol) was added dropwise through a constant pressure dropping funnel. After reacting for 6 hours, the temperature was raised to room temperature, the residue was removed by filtration, the filtrate was washed 6 times with deionized water, and the water layer was removed by a separatory funnel to retain the organic layer, and the solvent was further removed by rotary evaporation to obtain an allyl compound.

[0161] 2. Preparation of prepolymer glue

[0162] 60g of the above-mentioned allyl compound, 100g of 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 4g of diethyl allyl phosphate, 90g of toluene, 90g of cyclohexanone and 150g of butanone were added into a three-necked flask in sequence, heated to 130°C for reaction for 2 hours under continuous nitrogen flow and stirring, then further heated to 160°C for continued reaction for 2 hours, cooled to room temperature, added with 246g of surface-grafted acrylate silica microspheres, and continued stirring for 2 hours to obtain a prepolymer glue solution.

[0163] 3. Preparation of prepreg and laminate

[0164] Same as Example 1.

[0165] Embodiment 11

[0166] This embodiment provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, and the steps are as follows:

[0167] 1. Preparation of allyl compounds

[0168] 80 g of magnolol (about 0.3 mol) and 64 g of sodium carbonate were added to a three-necked flask containing 500 g of chloroform in sequence, placed in an ice bath (0°C) and continuously stirred and nitrogen was passed through, and then 80 g of trifluoroacetyl chloride (about 0.6 mol) was added dropwise through a constant pressure dropping funnel. After reacting for 6 hours, the temperature was raised to room temperature, and the residue was removed by filtration. The filtrate was washed 6 times with deionized water, and the water layer was removed by a separatory funnel to retain the organic layer, and the solvent was further removed by rotary evaporation to obtain an allyl compound.

[0169] 2. Preparation of prepolymer glue

[0170] 80g of the above-mentioned allyl compound, 140g of N,N'-m-phenylene bismaleimide, 6g of diethyl allyl phosphate, 130g of toluene, 130g of cyclohexanone and 180g of butanone were added into a three-necked flask in sequence, heated to 130°C for reaction for 2 hours under continuous nitrogen flow and stirring, then further heated to 160°C for continued reaction for 2 hours, cooled to room temperature, added 339g of surface-grafted acrylate silica microspheres, and continued stirring for 2 hours to obtain a prepolymer glue solution.

[0171] 3. Preparation of prepreg and laminate

[0172] Same as Example 1.

[0173] Example 12

[0174] This embodiment provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, and the steps are as follows:

[0175] 1. Preparation of allyl compounds

[0176] 120 g of magnolol (about 0.45 mol) and 125 g of potassium carbonate were added in sequence to a three-necked flask containing 700 g of chloroform, placed in an ice bath (0°C) and continuously stirred and nitrogen was passed through, and then 120 g of trifluoroacetyl chloride (about 0.9 mol) was added dropwise through a constant pressure dropping funnel. After reacting for 6 hours, the temperature was raised to room temperature, and the residue was removed by filtration. The filtrate was washed 6 times with deionized water, and the water layer was removed by a separatory funnel to retain the organic layer, and the solvent was further removed by rotary evaporation to obtain an allyl compound.

[0177] 2. Preparation of prepolymer glue

[0178] 120g of the above-mentioned allyl compound, 220g of N,N'-(4,4'-methylenediphenyl)bismaleimide, 10g of allyl dimethyl phosphate, 180g of toluene, 180g of cyclohexanone and 320g of butanone were added into a three-necked flask in sequence, heated to 130°C for reaction for 2 hours under continuous nitrogen flow and stirring, then further heated to 160°C for continued reaction for 2 hours, cooled to room temperature, added 525g of surface-grafted acrylate silica microspheres, and continued stirring for 2 hours to obtain a prepolymer glue solution.

[0179] 3. Preparation of prepreg and laminate

[0180] Same as Example 1.

[0181] Embodiment 13

[0182] This embodiment provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, and the steps are as follows:

[0183] 1. Preparation of allyl compounds

[0184] 120 g of 2,2'-diallyl bisphenol A (about 0.39 mol) and 79 g of triethylamine were added to a three-necked flask containing 800 g of chloroform in sequence, placed in an ice bath (0°C) and continuously stirred and nitrogen was passed through, and then 143 g of pentafluoropropionyl chloride (about 0.78 mol) was added dropwise through a constant pressure dropping funnel. After reacting for 6 hours, the temperature was raised to room temperature, the residue was removed by filtration, the filtrate was washed 6 times with deionized water, and the water layer was removed by a separatory funnel to retain the organic layer, and the solvent was further removed by rotary evaporation to obtain an allyl compound.

[0185] 2. Preparation of prepolymer glue

[0186] 150g of the above-mentioned allyl compound, 180g of N,N'-(4,4'-methylenediphenyl)bismaleimide, 8g of allyl diisopropyl phosphate, 180g of toluene, 180g of cyclohexanone and 300g of butanone were added into a three-necked flask in sequence, heated to 130°C for reaction for 2 hours under continuous nitrogen flow and stirring, then further heated to 160°C for continued reaction for 2 hours, cooled to room temperature, added 507g of surface-grafted acrylate silica microspheres, and continued stirring for 2 hours to obtain a prepolymer glue solution.

[0187] 3. Preparation of prepreg and laminate

[0188] Same as Example 1.

[0189] Comparative Example 1

[0190] This comparative example provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, which are basically the same as Example 1, except that no allyl compound is prepared. The steps are as follows:

[0191] 1. Preparation of glue

[0192] 150g 3,3'-diallyl bisphenol S, 220g N,N'-(4,4'-methylenediphenyl) bismaleimide, 10g diethyl allyl phosphate, 200g toluene, 200g cyclohexanone and 330g butanone were added into a three-necked flask in sequence, and stirred continuously until completely dissolved. Then, 570g surface-grafted acrylate silica microspheres were added, and stirring was continued for 2 hours to obtain a glue solution.

[0193] 2. Preparation of prepreg and laminate

[0194] Same as Example 1.

[0195] Comparative Example 2

[0196] This comparative example provides an allyl compound and a preparation method thereof, a prepolymer glue and a preparation method thereof, a prepreg and a preparation method thereof, and a laminate and a preparation method thereof, which are basically the same as Example 7, except that: no allyl compound is prepared. The steps are as follows:

[0197] 1. Preparation of glue

[0198] 220g of 2,2'-diallyl bisphenol A, 240g of 1,1'-(2,2,4-trimethyl-1,6-hexanediyl)bis-1H-pyrrole-2,5-dione, 12g of triallyl phosphate, 250g of toluene, 250g of cyclohexanone and 410g of butanone were added into a three-necked flask in sequence, and stirred continuously until completely dissolved. Then, 708g of surface-grafted acrylate silica microspheres were added, and stirring was continued for 2 hours to obtain a glue solution.

[0199] 2. Preparation of prepreg and laminate

[0200] Same as Example 7.

[0201] The following tests were performed on the laminated boards of the above embodiments and comparative examples:

[0202] Test method:

[0203] (1) The copper foil on the laminate was peeled off and then the dielectric constant Dk and dielectric loss Df were measured at a frequency of 10 GHz using a KEYSIGHT N5224B vector network analyzer from the United States. The test results are shown in Table 1.

[0204] (2) The glass transition temperature of the laminate with the copper foil removed was measured using a TA company model DMA850 dynamic mechanical analyzer. The test conditions were: 3°C / min, heating from 50°C to 350°C, frequency of 1HZ, and deformation of 20μm. The test results are shown in Table 1.

[0205] Table 1

[0206]

[0207] It can be seen from Table 1 that in Comparative Examples 1 and 2, directly using 3,3'-diallyl bisphenol S and 2,2'-diallyl bisphenol A to modify and toughen the bismaleimide resin will affect the dielectric properties of the bismaleimide material, increasing its dielectric constant and dielectric loss, especially the dielectric loss is not less than 0.0109.

[0208] In Examples 1 to 13, fluorine-containing acyl chloride is reacted with the compound of formula II to prepare an allyl compound. After the bismaleimide resin is modified by the allyl compound and then prepared into a laminate, the dielectric properties are optimized, especially the dielectric loss is less than 0.0079. At the same time, although the glass transition temperature in the examples is slightly decreased, it is still more than 240°C, which meets the application and processing requirements of high-frequency and high-speed packaging carriers.

[0209] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0210] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the attached claims.

Claims

1. An allyl compound, characterized in that: It has the structure shown in Formula I: Formula I; Wherein, L is selected from a single bond, -CH2-, -S(=O)(=O)- or -C(CH3)(CH3)-; and R is selected from a fluorine-substituted C1-C8 alkyl group.

2. The allyl compound according to claim 1, characterized in that: It has a structure shown in any one of formula (I-1) to formula (I-2): Formula (I-1) Formula (I-2).

3. The allyl compound according to any one of claims 1 to 2, characterized in that: R is selected from perfluoro-substituted C1-C8 alkyl groups.

4. A method for preparing an allyl compound, characterized in that: The following steps are involved: Mixing a compound of formula II, a compound of formula III, an acid-binding agent and a solvent to react and generate a compound of formula II; Formula II; Formula III; Formula I; Wherein, L is selected from a single bond, -CH2-, -S(=O)(=O)- or -C(CH3)(CH3)-; and R is selected from a fluorine-substituted C1-C8 alkyl group.

5. The method for preparing an allyl compound according to claim 4, characterized in that: Includes at least one of the following features: (1) The compound of formula II is at least one selected from 3,3'-diallylbisphenol S, 2,2'-diallylbisphenol A and magnolol; (2) the compound of formula III is at least one selected from trifluoroacetyl chloride, pentafluoropropionyl chloride, heptafluorobutyryl chloride, nonafluoropentanoyl chloride, undecafluorohexanoyl chloride, tridecafluoroheptanoyl chloride, pentafluorooctanoyl chloride and heptadecafluorononanoyl chloride; (3) The molar ratio of the compound of formula II to the compound of formula III is 1:(1.5-2.5).

6. The method for preparing an allyl compound according to any one of claims 4 to 5, characterized in that: Includes at least one of the following features: (1) The acid binding agent comprises at least one of potassium carbonate, sodium carbonate and triethylamine; (2) The mass of the acid binding agent accounts for 20% to 60% of the total mass of the compound of formula II and the compound of formula III; (3) The solvent includes chloroform; (4) The reaction temperature is -10℃~10℃; (5) The reaction time is 4h~8h.

7. A bismaleimide resin composition, characterized in that: The invention comprises a bismaleimide resin and the allyl compound according to any one of claims 1 to 6.

8. The bismaleimide resin composition according to claim 7, characterized in that: Also included are acrylic-containing flame retardants, fillers and solvents.

9. The bismaleimide resin composition according to claim 8, characterized in that: Includes at least one of the following features: (1) The weight of the bismaleimide resin is 100-240 parts; the weight of the allyl compound is 60-220 parts; the weight of the acryl-containing flame retardant is 4-12 parts; the weight of the filler is 246-708 parts and the weight of the solvent is 330-910 parts; (2) The bismaleimide resin includes at least one of N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N'-m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 1,1-(4-methyl-1,3-phenylene)bis-1H-pyrrole-2,5-dione and 1,1'-(2,2,4-trimethyl-1,6-hexanediyl)bis-1H-pyrrole-2,5-dione; (3) The acryl-containing flame retardant includes at least one of diethyl allyl phosphate, dimethyl allyl phosphate, diisopropyl allyl phosphate, triallyl phosphate and diethyl (2-methylallyl) phosphonate; (4) The filler comprises silica microspheres grafted with acrylate on the surface; (5) The solvent includes at least one of toluene, cyclohexanone, butanone and acetone.

10. A prepolymer glue, characterized in that: The raw material comprises the bismaleimide resin composition described in any one of claims 7 to 9.

11. A method for preparing the prepolymer glue according to claim 10, characterized in that: The following steps are involved: The bismaleimide resin and the allyl compound are polymerized.

12. A prepreg, characterized in that: The raw materials include reinforcing material and the prepolymer glue solution as claimed in claim 10.

13. A laminated board, characterized in that: The raw materials include metal foil and the prepreg according to claim 12, or include metal foil and the prepolymer glue according to claim 10.

Images