Allyl compounds and their preparation methods, bismaleimide resin compositions and their applications

Abstract

This application relates to the field of semiconductor technology, and particularly to an allyl compound and its preparation method, a bismaleimide resin composition, and its applications. An allyl compound has the structure shown in Formula I. When the compound with the above structure reacts with bismaleimide resin, it forms a larger porous structure within the bismaleimide material, increasing the internal free volume of the material. This significantly reduces the dielectric constant and dielectric loss of the bismaleimide material, enabling it to be used as a low-dielectric packaging substrate material in high-frequency, high-speed communication applications. Formula I.

Description

Technical Field

[0001] This application relates to the field of semiconductor technology, and in particular to an allyl compound and its preparation method, a bismaleimide resin composition and its application. Background Technology

[0002] In the era of high frequency and high speed, low-dielectric materials are a hot research topic. Among them, low-dielectric packaging substrate materials are particularly challenging due to their high performance requirements and development difficulties, and are currently mainly controlled by a few foreign giants. Therefore, the development of low-dielectric packaging substrate materials is of great strategic significance to the development of my country's semiconductor packaging industry.

[0003] Bismaleimide is a crucial material in semiconductor packaging, especially as a key raw material for packaging substrates. Its unique imide rings ensure excellent heat resistance and dimensional stability. However, bismaleimide is brittle and has low solubility. To address these issues, chain extension modifications of bismaleimide resins using DABPA, DABPS, DDS, and DDM have been reported. However, the resulting materials exhibit high dielectric loss, limiting the application of bismaleimide in high-frequency and high-speed applications. Summary of the Invention

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

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

[0006] Formula I;

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

[0008] The second aspect of this application provides a method for preparing allyl compounds, the technical solution of which is as follows:

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

[0010] A mixture of compound II, compound III, acid-binding agent, and solvent reacts to produce compound II;

[0011] Formula II; Formula III;

[0012] Formula I;

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

[0014] A third aspect of this application provides a bismaleimide resin composition, the technical solution of which is as follows:

[0015] A bismaleimide resin composition comprising a bismaleimide resin and an allyl compound as described above.

[0016] The fourth aspect of this application provides a prepolymer adhesive whose raw materials include the bismaleimide resin composition described above.

[0017] The fifth aspect of this application provides a method for preparing a prepolymer adhesive, the technical solution of which is as follows:

[0018] A method for preparing a prepolymer adhesive includes the following steps:

[0019] The bismaleimide resin and allyl compounds undergo a polymerization reaction.

[0020] The sixth aspect of this application provides a semi-cured sheet whose raw materials include reinforcing materials and prepolymer adhesive as described above.

[0021] The seventh aspect of this application provides a laminate whose raw materials include metal foil and the prepreg as described above, or include metal foil and the prepolymer liquid as described above.

[0022] Compared with traditional solutions, this application has the following advantages:

[0023] The allyl compounds provided in this application contain fluorine atoms. Fluorine atoms have a strong electron-withdrawing ability, making it difficult for carbon-fluorine bonds to be polarized. At the same time, the strong repulsion between fluorine atoms will hinder the stacking between chain segments. After the above-mentioned compounds react with bismaleimide resin, they will form a larger loose structure inside the bismaleimide material, increasing the free volume inside the material. This can significantly reduce the dielectric constant and dielectric loss of the bismaleimide material, making the bismaleimide material usable as a low-dielectric packaging substrate material in the field of high-frequency and high-speed communication. Detailed Implementation

[0024] The present application will be further described in detail below with reference to specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0026] the term

[0027] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:

[0028] In this application, the terms "optionally," "optionally," and "optional" refer to options that are optional, meaning they can be selected from either "with" or "without." If multiple "optional" options appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "optional" option is independent.

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

[0030] In this application, numerical intervals (i.e. numerical ranges) are involved. Unless otherwise specified, the selected numerical distributions within the above-mentioned numerical intervals are considered continuous, and include the two numerical endpoints (i.e., the minimum value and the maximum value) of the numerical range, as well as every value between the two numerical endpoints.

[0031] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.

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

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

[0034] Formula I;

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

[0036] The aforementioned allyl compounds contain fluorine atoms. Fluorine atoms have a strong electron-withdrawing ability, making it difficult for carbon-fluorine bonds to be polarized. At the same time, the strong repulsion between fluorine atoms hinders the stacking between chain segments. When the compounds with the above structure react with bismaleimide resin, they form a larger porous structure inside the bismaleimide material, increasing the free volume inside the material. This can significantly reduce the dielectric constant and dielectric loss of the bismaleimide material, making it suitable as a low-dielectric packaging substrate material for high-frequency and high-speed communication applications.

[0037] Alternatively, the allyl compounds have the structures shown in any of formulas (I-1) to (I-2):

[0038] Formula (I-1)

[0039] Formula (I-2).

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

[0041] The second aspect of this application provides a method for preparing allyl compounds, the technical solution of which is as follows:

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

[0043] A mixture of compound II, compound III, acid-binding agent, and solvent reacts to produce compound II;

[0044] Formula II; Formula III;

[0045] Formula I;

[0046] As mentioned above, L and R will not be repeated here.

[0047] The above preparation method removes the highly polar hydroxyl group by reacting a fluorinated acyl chloride with the hydroxyl group of the compound of formula II, while simultaneously introducing fluorine atoms. The strong electron-withdrawing ability of fluorine atoms makes it difficult to polarize the carbon-fluorine bond, and the strong repulsion between fluorine atoms hinders the stacking of chain segments. Reacting the prepared allyl compound with bismaleimide resin creates a larger porous structure within the maleimide material, increasing the internal free volume and significantly reducing the dielectric constant and dielectric loss of the two materials. This allows the bismaleimide material to be used as a low-dielectric packaging substrate material in high-frequency, high-speed communication applications.

[0048] Optionally, the compound of formula II is selected from at least one of 3,3'-diallylbisphenol S, 2,2'-diallylbisphenol A, and magnolol. The structural formula of 3,3'-diallylbisphenol S is: The structural formula of 2,2'-diallylbisphenol 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, pentadecanofluorooctanoyl 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 ratios are 1:1.5, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, and 1:2.5.

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

[0052] Optionally, 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, it accounts for 20%, 30%, 40%, and 50% of the total mass.

[0053] In some embodiments, the raw materials contain 60 to 150 parts by weight of compound II, 71 to 346 parts by weight of compound III, and 37 to 125 parts by weight of acid-binding agent.

[0054] Optionally, the solvent includes chloroform.

[0055] Optionally, the reaction temperature is -10℃ to 10℃. For example, the reaction temperatures are -10℃, -5℃, -2℃, 0℃, 2℃, 5℃, and 10℃.

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

[0057] The raw materials used in the above preparation methods have all been industrially produced, are inexpensive and readily available, have simple chemical synthesis reactions, involve fewer steps, are easy to industrialize, and can be applied to existing production lines.

[0058] A third aspect of this application provides a bismaleimide resin composition, the technical solution of which is as follows:

[0059] A bismaleimide resin composition comprising a bismaleimide resin and an allyl compound as described above.

[0060] In the above-mentioned bismaleimide resin composition, allyl compounds can further undergo an olefin reaction with the bismaleimide resin to obtain a linear prepolymer. The generation of a linear prepolymer through the olefin reaction can significantly reduce the dielectric properties of the bismaleimide material while ensuring processability, and solves the problems of low solubility and poor toughness of bismaleimide resin.

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

[0062] Optionally, the bismaleimide resin comprises at least one selected from N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N'-m-phenylenebismaleimide, 2,2'-bis[4-(4-maleiminophenoxy)phenyl]propane, bis(3-ethyl-5-methyl-4-maleiminophenyl)methane, 1,1-(4-methyl-1,3-phenylene)bis-1H-pyrrole-2,5-dione, and 1,1'-(2,2,4-trimethyl-1,6-hexadiyl)bis-1H-pyrrole-2,5-dione.

[0063] Optionally, the bismaleimide resin composition may also include a flame retardant, filler, and solvent containing a propylene group.

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

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

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

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

[0068] The fourth aspect of this application provides a prepolymer adhesive whose raw materials include the bismaleimide resin composition described above.

[0069] The fifth aspect of this application provides a method for preparing a prepolymer adhesive, the technical solution of which is as follows:

[0070] A method for preparing a prepolymer adhesive includes the following steps:

[0071] The bismaleimide resin and allyl compounds undergo a polymerization reaction.

[0072] Allyl compounds undergo polymerization with bismaleimide resin to obtain linear prepolymers. By extending the chain through prepolymerization, compared with simple blending, the dielectric properties of bismaleimide materials are significantly reduced while ensuring processability, and the problems of low solubility and poor toughness of bismaleimide resins are solved.

[0073] Optionally, the bismaleimide resin composition further includes a flame retardant containing an propylene group, a filler, and a solvent, to cause the bismaleimide resin and the allyl compound to undergo a polymerization reaction, including the following steps:

[0074] The bismaleimide resin, allyl compounds, propylene-containing flame retardants, and solvents are mixed and polymerized, and then the filler is added.

[0075] The above polymerization reaction does not require purification, the operation is simple, it saves a lot of solvent, and it is easy to realize industrial production.

[0076] Optionally, the polymerization reaction includes the following procedure: reacting at 120℃~140℃ for 1h~3h, and then raising the temperature to 150℃~170℃ to continue the reaction for 1h~3h.

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

[0078] The sixth aspect of this application provides a semi-cured sheet whose raw materials include reinforcing materials and prepolymer adhesive as described above.

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

[0080] The aforementioned semi-cured sheet can be prepared by impregnating the reinforcing material in a prepolymer solution.

[0081] The seventh aspect of this application provides a laminate whose raw materials include metal foil and the prepreg as described above, or include metal foil and the prepolymer liquid as described above.

[0082] The allyl compounds provided in this application, when used in prepolymerization and chain extension with bismaleimide resin, improve the solubility and toughness of bismaleimide materials while reducing the dielectric constant and loss of bismaleimide materials, thus meeting the stringent requirements for packaging substrate materials in high-frequency and high-speed applications.

[0083] The following description is further illustrated with specific embodiments and comparative examples. Unless otherwise specified, the raw materials involved in the following specific embodiments and comparative examples are all commercially available. Unless otherwise specified, the instruments used are all commercially available. Unless otherwise specified, the processes involved are conventionally selected by those skilled in the art.

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

[0085] Example 1

[0086] This embodiment provides an allyl compound and its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method. The steps are as follows:

[0087] 1. Preparation of allyl compounds

[0088] 150 g of 3,3'-diallylbisphenol S (approximately 0.45 mol) and 125 g of potassium carbonate were sequentially added to a three-necked flask containing 800 g of chloroform. The flask was placed in an ice bath (0 °C) and continuously stirred and purged with nitrogen. Then, 121 g of trifluoroacetyl chloride (approximately 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, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, and the organic layer was retained. The solvent was then removed by rotary evaporation to obtain allyl compounds.

[0089] 2. Preparation of prepolymer adhesive

[0090] 150g of the above allyl compounds, 220g of N,N'-(4,4'-methylenediphenyl)bismaleimide, 10g of allyl phosphate diethyl ester, 200g of toluene, 200g of cyclohexanone, and 330g of butanone were sequentially added to a three-necked flask. Under continuous nitrogen purging and stirring, the mixture was heated to 130°C and reacted for 2 hours. Then, the temperature was further increased to 160°C and the reaction was continued for 2 hours. After cooling to room temperature, 570g of surface-grafted acrylate silica microspheres were added, and the mixture was stirred for another 2 hours to obtain the prepolymer solution.

[0091] 3. Preparation of prepreg and laminate

[0092] 2116 fiberglass cloth (basic weight 105g / m) 2 The prepreg was immersed in the above prepolymer solution, removed, and baked in an oven at 185°C for 4 minutes to obtain a prepreg with a resin content of 50wt%. Eight prepregs were stacked together, covered with 18-micron electrolytic copper foil, and placed in a vacuum press with a pressure of 28 kgf / cm². 2 The laminate is pressed at 200℃ for 2 hours, then heated to 220℃ and pressed for another hour. Finally, it is cooled and removed to obtain a laminate with a thickness of 0.85mm.

[0093] Example 2

[0094] This embodiment provides an allyl compound and its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method. The steps are as follows:

[0095] 1. Preparation of allyl compounds

[0096] 100g of 2,2'-diallylbisphenol A (approximately 0.325mol) and 69g of sodium carbonate were sequentially added to a three-necked flask containing 650g of chloroform. The flask was placed in an ice bath (0°C) and continuously stirred and purged with nitrogen. Then, 119g of pentafluoropropionyl chloride (approximately 0.65mol) was added dropwise through a constant-pressure dropping funnel. After reacting for 6 hours, the mixture was heated to room temperature, filtered to remove the residue, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed through a separatory funnel, leaving the organic layer. The solvent was then removed by rotary evaporation to obtain allyl compounds.

[0097] 2. Preparation of prepolymer adhesive

[0098] 100g of the above allyl compounds, 160g of N,N'-m-phenylenebismaleimide, 8g of allyl phosphate dimethyl ester, 150g of toluene, 150g of cyclohexanone, and 220g of butanone were sequentially added to a three-necked flask. Under continuous nitrogen purging and stirring, the mixture was heated to 130°C and reacted for 2 hours. Then, the temperature was further increased to 160°C and the reaction was continued for 2 hours. After cooling to room temperature, 402g of surface-grafted acrylate silica microspheres were added, and the mixture was stirred for another 2 hours to obtain the prepolymer solution.

[0099] 3. Preparation of prepreg and laminate

[0100] Same as Example 1.

[0101] Example 3

[0102] This embodiment provides an allyl compound and its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method. The steps are as follows:

[0103] 1. Preparation of allyl compounds

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

[0105] 2. Preparation of prepolymer adhesive

[0106] 80g of the above allyl compounds, 120g of 2,2'-bis[4-(4-maleimide phenoxy)phenyl]propane, 6g of allyl phosphate diisopropyl ester, 120g of toluene, 120g of cyclohexanone, and 160g of butanone were sequentially added to a three-necked flask. Under continuous nitrogen purging and stirring, the mixture was heated to 130°C and reacted for 2 hours. Then, the temperature was further increased to 160°C and the reaction was continued for 2 hours. After cooling to room temperature, 309g of surface-grafted acrylate silica microspheres were added, and the mixture was stirred for another 2 hours to obtain the prepolymer solution.

[0107] 3. Preparation of prepreg and laminate

[0108] Same as Example 1.

[0109] Example 4

[0110] This embodiment provides an allyl compound and its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method. The steps are as follows:

[0111] 1. Preparation of allyl compounds

[0112] 90g of magnolol (approximately 0.34 mol) and 68g of triethylamine were sequentially added to a three-necked flask containing 850g of chloroform. The flask was placed in an ice bath (0°C) and continuously stirred and purged with nitrogen. Then, 192g of nonafluoropentanoyl chloride (approximately 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, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, leaving the organic layer. The solvent was then removed by rotary evaporation to obtain allyl compounds.

[0113] 2. Preparation of prepolymer adhesive

[0114] 120g of the above allyl compounds, 160g of bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane, 8g of triallyl phosphate, 160g of toluene, 160g of cyclohexanone, and 340g of butanone were sequentially added to a three-necked flask. Under continuous nitrogen purging and stirring, the mixture was heated to 130°C and reacted for 2 hours. Then, the temperature was further increased to 160°C and the reaction was continued for 2 hours. After cooling to room temperature, 432g of surface-grafted acrylate silica microspheres were added, and the mixture was stirred for another 2 hours to obtain the prepolymer solution.

[0115] 3. Preparation of prepreg and laminate

[0116] Same as Example 1.

[0117] Example 5

[0118] This embodiment provides an allyl compound and its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method. The steps are as follows:

[0119] 1. Preparation of allyl compounds

[0120] 80g of magnolol (approximately 0.3 mol) and 65g of sodium carbonate were sequentially added to a three-necked flask containing 850g of chloroform. The flask was placed in an ice bath (0°C) and continuously stirred and purged with nitrogen. Then, 200g of undecanoyl chloride (approximately 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, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed through a separatory funnel, leaving the organic layer. The solvent was then removed by rotary evaporation to obtain allyl compounds.

[0121] 2. Preparation of prepolymer adhesive

[0122] 100g of the above allyl compounds, 140g of 1,1-(4-methyl-1,3-phenylene)di-1H-pyrrole-2,5-dione, 6g of (2-methylallyl)phosphonate diethyl ester, 140g of toluene, 140g of cyclohexanone, and 200g of butanone were sequentially added to a three-necked flask. Under continuous nitrogen purging and stirring, the mixture was heated to 130°C and reacted for 2 hours. Then, the temperature was further increased to 160°C and the reaction was continued for 2 hours. After cooling to room temperature, 369g of surface-grafted acrylate silica microspheres were added, and the mixture was stirred for another 2 hours to obtain the prepolymer solution.

[0123] 3. Preparation of prepreg and laminate

[0124] Same as Example 1.

[0125] Example 6

[0126] This embodiment provides an allyl compound and its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method. The steps are as follows:

[0127] 1. Preparation of allyl compounds

[0128] 120 g of magnolol (approximately 0.45 mol) and 125 g of potassium carbonate were sequentially added to a three-necked flask containing 1400 g of chloroform. The flask was placed in an ice bath (0 °C) and continuously stirred and purged with nitrogen. Then, 346 g of tridecafluoroheptanoyl chloride (approximately 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, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, leaving the organic layer. The solvent was then removed by rotary evaporation to obtain allyl compounds.

[0129] 2. Preparation of prepolymer adhesive

[0130] 200g of the above allyl compounds, 220g of 1,1'-(2,2,4-trimethyl-1,6-hexadiyl)bis-1H-pyrrole-2,5-dione, 10g of (2-methylallyl)phosphonate diethyl ester, 220g of toluene, 220g of cyclohexanone, and 390g of butanone were sequentially added to a three-necked flask. Under continuous nitrogen purging and stirring, the mixture was heated to 130°C and reacted for 2 hours. Then, the temperature was further increased to 160°C and the reaction was continued for 2 hours. After cooling to room temperature, 645g of surface-grafted acrylate silica microspheres were added, and the mixture was stirred for another 2 hours to obtain the prepolymer solution.

[0131] 3. Preparation of prepreg and laminate

[0132] Same as Example 1.

[0133] Example 7

[0134] This embodiment provides an allyl compound and its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method. The steps are as follows:

[0135] 1. Preparation of allyl compounds

[0136] 150 g of 2,2'-diallylbisphenol A (approximately 0.485 mol) and 134 g of potassium carbonate were sequentially added to a three-necked flask containing 1400 g of chloroform. The flask was placed in an ice bath (0 °C) and continuously stirred and purged with nitrogen. Then, 324 g of undecanoyl chloride (approximately 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, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, leaving the organic layer. The solvent was then removed by rotary evaporation to obtain allyl compounds.

[0137] 2. Preparation of prepolymer adhesive

[0138] 220g of the above allyl compounds, 240g of 1,1'-(2,2,4-trimethyl-1,6-hexadiyl)bis-1H-pyrrole-2,5-dione, 12g of triallyl phosphate, 250g of toluene, 250g of cyclohexanone, and 410g of butanone were sequentially added to a three-necked flask. Under continuous nitrogen purging and stirring, the mixture was heated to 130°C and reacted for 2 hours. Then, the temperature was further increased to 160°C and the reaction was continued for 2 hours. After cooling to room temperature, 708g of surface-grafted acrylate silica microspheres were added, and the mixture was stirred for another 2 hours to obtain the prepolymer solution.

[0139] 3. Preparation of prepreg and laminate

[0140] Same as Example 1.

[0141] Example 8

[0142] This embodiment provides an allyl compound and its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method. The steps are as follows:

[0143] 1. Preparation of allyl compounds

[0144] 100g of 3,3'-diallylbisphenol S (approximately 0.3mol) and 64g of sodium carbonate were sequentially added to a three-necked flask containing 800g of chloroform. The flask was placed in an ice bath (0°C) and continuously stirred and purged with nitrogen. Then, 172g of nonafluoropentanoyl chloride (approximately 0.6mol) 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, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, and the organic layer was retained. The solvent was then removed by rotary evaporation to obtain allyl compounds.

[0145] 2. Preparation of prepolymer adhesive

[0146] 130g of the above allyl compounds, 140g of 1,1-(4-methyl-1,3-phenylene)di-1H-pyrrole-2,5-dione, 6g of allyl phosphate diisopropyl ester, 160g of toluene, 160g of cyclohexanone, and 220g of butanone were sequentially added to a three-necked flask. Under continuous nitrogen purging and stirring, the mixture was heated to 130°C and reacted for 2 hours. Then, the temperature was further increased to 160°C and the reaction was continued for 2 hours. After cooling to room temperature, 414g of surface-grafted acrylate silica microspheres were added, and the mixture was stirred for another 2 hours to obtain the prepolymer solution.

[0147] 3. Preparation of prepreg and laminate

[0148] Same as Example 1.

[0149] Example 9

[0150] This embodiment provides an allyl compound and its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method. The steps are as follows:

[0151] 1. Preparation of allyl compounds

[0152] 60 g of 3,3'-diallylbisphenol S (approximately 0.18 mol) and 37 g of triethylamine were sequentially added to a three-necked flask containing 450 g of chloroform. The flask was placed in an ice bath (0 °C) and continuously stirred and purged with nitrogen. Then, 85 g of heptafluorobutyryl chloride (approximately 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, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, retaining the organic layer. The solvent was then removed by rotary evaporation to obtain allyl compounds.

[0153] 2. Preparation of prepolymer adhesive

[0154] 60g of the above allyl compounds, 100g of bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane, 4g of allyl phosphate dimethyl ester, 90g of toluene, 90g of cyclohexanone and 150g of butanone were sequentially added to a three-necked flask. Under continuous nitrogen purging and stirring, the mixture was heated to 130°C and reacted for 2 hours. Then, the temperature was further increased to 160°C and the reaction was continued for 2 hours. After cooling to room temperature, 246g of surface-grafted acrylate silica microspheres were added, and the mixture was stirred for another 2 hours to obtain the prepolymer solution.

[0155] 3. Preparation of prepreg and laminate

[0156] Same as Example 1.

[0157] Example 10

[0158] This embodiment provides an allyl compound and its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method. The steps are as follows:

[0159] 1. Preparation of allyl compounds

[0160] 60 g of 2,2'-diallylbisphenol A (approximately 0.195 mol) and 39 g of triethylamine were sequentially added to a three-necked flask containing 400 g of chloroform. The flask was placed in an ice bath (0 °C) and continuously stirred and purged with nitrogen. Then, 71 g of pentafluoropropionyl chloride (approximately 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, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, retaining the organic layer. The solvent was then removed by rotary evaporation to obtain allyl compounds.

[0161] 2. Preparation of prepolymer adhesive

[0162] 60g of the above allyl compounds, 100g of 2,2'-bis[4-(4-maleimide phenoxy)phenyl]propane, 4g of allyl phosphate diethyl ester, 90g of toluene, 90g of cyclohexanone, and 150g of butanone were sequentially added to a three-necked flask. Under continuous nitrogen purging and stirring, the mixture was heated to 130°C and reacted for 2 hours. Then, the temperature was further increased to 160°C and the reaction was continued for 2 hours. After cooling to room temperature, 246g of surface-grafted acrylate silica microspheres were added, and the mixture was stirred for another 2 hours to obtain the prepolymer solution.

[0163] 3. Preparation of prepreg and laminate

[0164] Same as Example 1.

[0165] Example 11

[0166] This embodiment provides an allyl compound and its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method. The steps are as follows:

[0167] 1. Preparation of allyl compounds

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

[0169] 2. Preparation of prepolymer adhesive

[0170] 80g of the above allyl compounds, 140g of N,N'-m-phenylenebismaleimide, 6g of allyl phosphate diethyl ester, 130g of toluene, 130g of cyclohexanone, and 180g of butanone were sequentially added to a three-necked flask. Under continuous nitrogen purging and stirring, the mixture was heated to 130°C and reacted for 2 hours. Then, the temperature was further increased to 160°C and the reaction was continued for 2 hours. After cooling to room temperature, 339g of surface-grafted acrylate silica microspheres were added, and the mixture was stirred for another 2 hours to obtain the prepolymer solution.

[0171] 3. Preparation of prepreg and laminate

[0172] Same as Example 1.

[0173] Example 12

[0174] This embodiment provides an allyl compound and its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method. The steps are as follows:

[0175] 1. Preparation of allyl compounds

[0176] 120 g of magnolol (approximately 0.45 mol) and 125 g of potassium carbonate were sequentially added to a three-necked flask containing 700 g of chloroform. The flask was placed in an ice bath (0 °C) and continuously stirred and purged with nitrogen. Then, 120 g of trifluoroacetyl chloride (approximately 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, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, leaving the organic layer. The solvent was then removed by rotary evaporation to obtain allyl compounds.

[0177] 2. Preparation of prepolymer adhesive

[0178] 120g of the above allyl compounds, 220g of N,N'-(4,4'-methylenediphenyl)bismaleimide, 10g of allyl phosphate dimethyl ester, 180g of toluene, 180g of cyclohexanone, and 320g of butanone were sequentially added to a three-necked flask. Under continuous nitrogen purging and stirring, the mixture was heated to 130°C and reacted for 2 hours. Then, the temperature was further increased to 160°C and the reaction was continued for 2 hours. After cooling to room temperature, 525g of surface-grafted acrylate silica microspheres were added, and the mixture was stirred for another 2 hours to obtain the prepolymer solution.

[0179] 3. Preparation of prepreg and laminate

[0180] Same as Example 1.

[0181] Example 13

[0182] This embodiment provides an allyl compound and its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method. The steps are as follows:

[0183] 1. Preparation of allyl compounds

[0184] 120 g of 2,2'-diallylbisphenol A (approximately 0.39 mol) and 79 g of triethylamine were sequentially added to a three-necked flask containing 800 g of chloroform. The flask was placed in an ice bath (0 °C) and continuously stirred and purged with nitrogen. Then, 143 g of pentafluoropropionyl chloride (approximately 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, and the filtrate was washed 6 times with deionized water. The aqueous layer was removed by a separatory funnel, leaving the organic layer. The solvent was then removed by rotary evaporation to obtain allyl compounds.

[0185] 2. Preparation of prepolymer adhesive

[0186] 150g of the above allyl compounds, 180g of N,N'-(4,4'-methylenediphenyl)bismaleimide, 8g of allyl phosphate diisopropyl ester, 180g of toluene, 180g of cyclohexanone, and 300g of butanone were sequentially added to a three-necked flask. Under continuous nitrogen purging and stirring, the mixture was heated to 130°C and reacted for 2 hours. Then, the temperature was further increased to 160°C and the reaction was continued for 2 hours. After cooling to room temperature, 507g of surface-grafted acrylate silica microspheres were added, and the mixture was stirred for another 2 hours to obtain the prepolymer 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 its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method, which are basically the same as those in Example 1, except that the allyl compound was not prepared. The steps are as follows:

[0191] 1. Preparation of adhesive solution

[0192] 150g of 3,3'-diallylbisphenol S, 220g of N,N'-(4,4'-methylenediphenyl)bismaleimide, 10g of allyl phosphate diethyl ester, 200g of toluene, 200g of cyclohexanone and 330g of butanone were added sequentially to a three-necked flask and stirred continuously until completely dissolved. Then, 570g of surface-grafted acrylate silica microspheres were added and stirred for another 2 hours to obtain the adhesive 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 its preparation method, a prepolymer adhesive and its preparation method, a prepreg and its preparation method, and a laminate and its preparation method, which are basically the same as those in Example 7, except that the allyl compound was not prepared. The steps are as follows:

[0197] 1. Preparation of adhesive solution

[0198] 220g of 2,2'-diallylbisphenol A, 240g of 1,1'-(2,2,4-trimethyl-1,6-hexadiyl)bis-1H-pyrrole-2,5-dione, 12g of triallyl phosphate, 250g of toluene, 250g of cyclohexanone, and 410g of butanone were added sequentially to a three-necked flask 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 the adhesive solution.

[0199] 2. Preparation of prepreg and laminate

[0200] Same as Example 7.

[0201] The following tests were performed on the laminates 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. The test results are shown in Table 1.

[0204] (2) The glass transition temperature of the laminate after copper foil removal was measured using a TA DMA850 dynamic mechanical analyzer. The test conditions were: heating from 50℃ to 350℃ at a rate of 3℃ / min, a frequency of 1Hz, and a deformation of 20μm. The test results are shown in Table 1.

[0205] Table 1

[0206]

[0207] As shown in Table 1, in Comparative Examples 1 and 2, directly using 3,3'-diallylbisphenol S and 2,2'-diallylbisphenol A to modify and toughen bismaleimide resin will affect the dielectric properties of bismaleimide material, increasing its dielectric constant and dielectric loss, especially the dielectric loss, which is not less than 0.0109.

[0208] In Examples 1 to 13, fluorinated acyl chlorides were reacted with compounds of Formula II to prepare allyl compounds. After modifying bismaleimide resin with allyl compounds and subsequently preparing laminates, the dielectric properties were optimized, particularly the dielectric loss, which was below 0.0079. Meanwhile, although the glass transition temperatures in these examples decreased slightly, they still exceeded 240°C, meeting the application and processing requirements of high-frequency, high-speed packaging substrates.

[0209] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above 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 embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

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

2. The allyl compound according to claim 1, characterized in that, It has a structure shown in any of equations (I-1) to (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 perfluorinated C1-C8 alkyl groups.

4. A method for preparing an allyl compound, characterized in that, Includes the following steps: A mixture of compound II, compound III, acid-binding agent, and solvent reacts to produce compound I. Formula II; Formula III; Formula I; Wherein, L is selected from single bond, -CH2-, -S(=O)(=O)- or -C(CH3)(CH3)-; R is selected from fluorine-substituted C1-C8 alkyl groups.

5. The method for preparing allyl compounds according to claim 4, characterized in that, Includes at least one of the following features: (1) The compound of formula II is selected from at least one of 3,3'-diallylbisphenol S, 2,2'-diallylbisphenol A and magnolol; (2) The compound of formula III is selected from at least one of trifluoroacetyl chloride, pentafluoropropionyl chloride, heptafluorobutyryl chloride, nonafluoropentanoyl chloride, undecafluorohexanoyl chloride, tridecafluoroheptanoyl chloride, pentadecanofluorooctanoyl 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 the 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 includes 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 is chloroform; (4) The reaction temperature is -10℃ to 10℃; (5) The reaction time is 4h~8h.

7. A bismaleimide resin composition, characterized in that, Including bismaleimide resins and allyl compounds according to any one of claims 1 to 6.

8. The bismaleimide resin composition according to claim 7, characterized in that, It also includes flame retardants, fillers, and solvents containing propylene.

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

10. A prepolymer adhesive, characterized in that, Its raw materials include the bismaleimide resin composition according to any one of claims 7 to 9.

11. A method for preparing the prepolymer adhesive according to claim 10, characterized in that, Includes the following steps: The bismaleimide resin and allyl compounds undergo a polymerization reaction.

12. A semi-cured sheet, characterized in that, Its raw materials include reinforcing materials and the prepolymer liquid as described in claim 10.

13. A laminate, characterized in that, Its raw materials include metal foil and the prepreg as described in claim 12, or include metal foil and the prepolymer liquid as described in claim 10.

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