CN116102587A - Preparation method of silane modified diallyl bisphenol compound - Google Patents
Preparation method of silane modified diallyl bisphenol compound Download PDFInfo
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- CN116102587A CN116102587A CN202111326165.4A CN202111326165A CN116102587A CN 116102587 A CN116102587 A CN 116102587A CN 202111326165 A CN202111326165 A CN 202111326165A CN 116102587 A CN116102587 A CN 116102587A
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- diallyl bisphenol
- bisphenol compound
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Abstract
The invention provides a preparation method of silane modified diallyl bisphenol compound, which utilizes diallyl bisphenol compound with double-end hydroxyl groups to react with silane with at least one alkoxy group and at least one functional group with a crosslinkable double bond at a terminal band so as to obtain the silane modified diallyl bisphenol compound with the functional group with the crosslinkable double bond at the terminal band.
Description
Technical Field
The invention relates to a preparation method of modified diallyl bisphenol compound, in particular to a preparation method of silane modified diallyl bisphenol compound.
Background
At present, no matter the industrial technology of the printed circuit board (Printed circuit board, PCB) is developed to high-frequency, high-speed and high-density packaging methods, the development trend of light, thin, portability and multifunction of products is corresponded, the wiring of the copper-clad plate is more and more densely and thinned between layers, and more stringent requirements are put on the impedance characteristics and reliability of a transmission line and the assembly and processing precision of components. Under the requirements of high frequency, high speed and miniaturization, the high frequency transmission and low loss materials will replace transmission lines comprehensively, and the requirements of high heat resistance, low moisture absorption, low dielectric property and good flame resistance for circuit substrates must be achieved.
The low Dk/Df materials commonly used in high frequency and high speed printed circuit boards mainly comprise low polarity polyphenylene oxide, polytetrafluoroethylene, hydrocarbon resin, polyimide, styrene-maleic anhydride copolymer and the like. The curing system mainly uses various vinyl groups (such as vinyl groups, acrylic groups and methyl acrylic groups) on resin molecules as crosslinking points, uses various multifunctional vinyl crosslinking agents in a glue formulation in a matching way, and enables the crosslinking agents to start a crosslinking reaction in the hot-pressing process through the addition of peroxide in the glue formulation, so that the glue is cured. Among them, polyphenylene ether has a high glass transition temperature, a low Dk/Df and a low water absorption, and is a material attracting attention in the field of research of high-frequency and high-speed electronics.
For the production of a laminate of a polyphenylene ether resin system, a polyphenylene ether resin is usually used in combination with a monomer compound of triallyl isocyanate (triallyl isocyanurate, TAIC) or triallyl cyanate (triallyl cyanurate, TAC) as a crosslinking agent. However, TAIC has a low boiling point, and is easily volatilized from the resin composition formulation during the manufacturing process of the laminate, which causes distortion of the formulation, and further causes abnormal characteristics of the finally obtained electronic material, while TAC has a higher boiling point, but enol-like small molecules generated after thermal decomposition can cause substantial improvement of Dk and Df, which is unfavorable for the electrical characteristics after curing.
Based on the above, a small molecule multifunctional crosslinking agent is developed, which has higher boiling point, is stable to heat and low in polarity, and can be matched with polyphenyl ether, polytetrafluoroethylene, hydrocarbon resin and other resins for use, so that a thermosetting resin formula system for 5G materials is provided, and the aim of development is needed by those skilled in the art.
Disclosure of Invention
The invention provides a preparation method of silane modified diallyl bisphenol compound, which is used for obtaining silane modified diallyl bisphenol compound with functional groups of crosslinkable double bonds at terminal bands so as to obtain better performance.
The process for producing a silane-modified diallyl bisphenol compound of the present invention is a process for producing the silane-modified diallyl bisphenol compound, wherein the synthesis reaction formula is represented by the reaction formula (1):
reaction type (1)
In the reaction formula (1), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R2 is a C1 to C6 alkyl group, R3 is a functional group having a crosslinkable double bond, n+m is a positive integer of 1 to 8, and a is a positive integer of 1 to 4.
In one embodiment of the invention, the functional groups bearing a crosslinkable double bond include propenyl, vinyl, acrylic or methacrylic groups.
In one embodiment of the invention, n+m is 2 or 3.
In one embodiment of the present invention, the reaction temperature of the reaction formula (1) is 100℃to 180 ℃.
In one embodiment of the present invention, the ratio of diallyl bisphenol compound to the dialkoxysilane comprising functional groups with crosslinkable double bonds, calculated as the molar ratio of hydroxyl groups of the diallyl bisphenol compound to alkoxy groups of the dialkoxysilane comprising functional groups with crosslinkable double bonds, is 1:0.5 to 1:4.0.
in one embodiment of the present invention, the catalyst of reaction formula (1) is used in an amount of 500ppm to 5000ppm relative to the weight of the diallyl bisphenol compound.
Based on the above, the present invention provides a method for preparing a silane-modified diallyl bisphenol compound, wherein the obtained silane-modified diallyl bisphenol compound has at least two reactive double bonds in structure, and can be subjected to a crosslinking reaction with modified polyphenylene ether to further increase the crosslinking density and form a cured resin with high crosslinking density, so that the silane-modified diallyl bisphenol compound can be used on a polyphenylene ether resin laminate, and can also be compounded with bismaleimide resin as a raw material to form a thermosetting resin composition with low shrinkage, high Tg, high heat resistance and low dielectric property.
Drawings
FIG. 1 is an IR spectrum of a silane-modified diallyl bisphenol compound of example 2.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are illustrative, and the present disclosure is not limited thereto.
In this document, a range from "one value to another value" is a shorthand way of referring individually to all the values in the range, which are avoided in the specification. Thus, recitation of a particular numerical range includes any numerical value within that range, as well as the smaller numerical range bounded by any numerical value within that range, as if the any numerical value and the smaller numerical range were written in the specification.
The invention provides a silane modified diallyl bisphenol compound, the structure of which is represented by a formula (1):
(1)
In formula (1), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R2 is a C1 to C6 alkyl group, R3 is a functional group bearing a crosslinkable double bond, n+m is a positive integer from 1 to 8, and n+m is preferably 2 or 3.
More specifically, in formula (1), R3 is a functional group with a crosslinkable double bond, and the functional group with a crosslinkable double bond may include an acryl (allyl), vinyl (vinyl), acrylic (acrylate) or methacrylic (methacrylate), but the present invention is not limited thereto. In addition, in the formula (1), R3 may be an oxygen atom or an oxygen atom. If R3 contains oxygen atoms, it is possible, for example, to attach an oxygen atom and then to attach a functional group having a crosslinkable double bond.
In addition to the above silane-modified diallyl bisphenol compound represented by the formula (1), the present invention also proposes another silane-modified diallyl bisphenol compound having a structure represented by the formula (2):
(2)
In formula (2), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R3 is a functional group with a crosslinkable double bond, and a is a positive integer from 1 to 4.
In more detail, in the formula (2), R3 is a functional group with a crosslinkable double bond, and the functional group with a crosslinkable double bond may include an acryl (allyl), vinyl (vinyl), acrylic (acrylate) or methacrylic (methacrylate), but the present invention is not limited thereto. In addition, in the formula (2), R3 may be an oxygen atom or an oxygen atom. If R3 contains oxygen atoms, it is possible, for example, to attach an oxygen atom and then to attach a functional group having a crosslinkable double bond.
Meanwhile, the invention also provides a preparation method of the silane modified diallyl bisphenol compound, which is used for preparing the silane modified diallyl bisphenol compound represented by the formula (1) and the formula (2), wherein the synthesis reaction formula is represented by the reaction formula (1):
reaction type (1)
In the formula (1), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R2 is a C1 to C6 alkyl group, R3 is a functional group having a crosslinkable double bond, n+m is a positive integer of 1 to 8, n+m is preferably 2 or 3, and a is a positive integer of 1 to 4.
More specifically, in the reaction formula (1), R3 is a functional group with a crosslinkable double bond, and the functional group with a crosslinkable double bond may include an acryl (allyl), vinyl (vinyl), acrylic (acrylate) or methacrylic (methacrylate), but the present invention is not limited thereto. In addition, in the reaction formula (1), R3 may be an oxygen atom or an oxygen atom. If R3 contains oxygen atoms, it is possible, for example, to attach an oxygen atom and then to attach a functional group having a crosslinkable double bond.
As shown in the above reaction formula (1), the present invention mainly uses diallyl bisphenol compound having hydroxyl groups at both ends and silane having at least one alkoxy group and at least one functional group having a crosslinkable double bond at the terminal, and the dealcoholization reaction is performed at high temperature under the action of a catalyst to obtain silane-modified diallyl bisphenol compounds having functional groups having crosslinkable double bonds at the terminal (i.e., silane-modified diallyl bisphenol compounds represented by the formula (1) and the formula (2)).
In this embodiment, the reaction temperature of the reaction formula (1) is, for example, 100℃to 180℃and preferably 130℃to 160℃for, for example, 2 hours to 15 hours. In more detail, the diallyl bisphenol compound and the silane having a functional group with a crosslinkable double bond may be reacted at the bottom of the reaction tank, or the diallyl bisphenol compound and the silane having a functional group with a crosslinkable double bond may be reacted at the bottom of the reaction tank using a feed by a dropping method for a period of time of, for example, 1 to 10 hours. The ratio of diallyl bisphenol compound to dialkoxysilane having a functional group having a crosslinkable double bond, calculated as the molar ratio of the hydroxyl groups of the diallyl bisphenol compound to the dialkoxysilane having a functional group having a crosslinkable double bond, is, for example, 1:0.5 to 1:4.0.
in this example, the catalyst of the reaction formula (1) is used in an amount of, for example, 500ppm to 5000ppm based on the weight of the diallyl bisphenol compound. The types of catalysts may include, but are not limited to, acid catalysts, base catalysts, metal compound catalysts, ester catalysts, or combinations thereof, preferably, for example, ethyl triphenylphosphine chloride (ETPPCl), ethyl triphenylphosphine bromide (ETPPBr), ethyl triphenylphosphine iodide (ETPPI), ethyl triphenylphosphine acetate (etppac), tetrabutylammonium bromide (TBAB), triphenylphosphine (TPP), or tetra-n-butylammonium acetate (TBAAc), but the invention is not limited thereto.
In the reaction formula (1), the alkoxysilane having a functional group having a crosslinkable double bond used in the present invention is represented by the formula (a):
as described above, in the formula (a), R1 is a linear or branched C1 to C6 alkyl or aryl, R2 is a C1 to C6 alkyl, R3 is a functional group with a crosslinkable double bond, and the functional group with a crosslinkable double bond may include acryl (allyl), vinyl (vinyl), acryl (acrylate) or methacrylate (methacrylate), but the present invention is not limited thereto. In the present embodiment, specific examples of the formula (a) may include methyl vinyl dimethoxy silane, methyl vinyl diethoxy silane, allyl methyl dimethoxy silane, 1-allyl-2, 2-dimethoxy-1, 2-aza-cyclopentane or a combination thereof, but the invention is not limited thereto. The chemical structural formula of the specific case is shown as follows:
1- (methacryloxymethyl) methyldimethoxysilane
3- (methacryloxypropyl) methyldimethoxysilane
The silane-modified diallyl bisphenol compound proposed in the present invention will be described in detail below with reference to experimental examples. However, the following experimental examples are not intended to limit the present invention.
Experimental example
In order to demonstrate that the preparation process proposed in the present invention can obtain silane-modified diallyl bisphenol compounds, this experiment is particularly described below.
Example 1
50.19g of diallyl bisphenol A (purity > 90%) and 0.042g of ethyl triphenylphosphine acetate are added into a reaction tank to be stirred uniformly with 51.64g of methyl vinyl dimethoxy silane (XL 12, wacker in Germany), and the mixture is heated to 110 ℃ to react for 7 hours, thus obtaining the silane modified diallyl bisphenol compound.
Example 2
72.3g of diallyl bisphenol A (purity > 90%) is placed in a four-mouth round bottom flask, stirred and heated to 145 ℃, 0.125g of tetra-n-butyl ammonium acetate is added, 58.3g of methyl vinyl dimethoxy silane (XL 12, wacker in Germany) is added dropwise into a reaction tank after being stirred uniformly, the dropwise adding time is 3 hours, methanol liquid generated in the reaction process is collected, and the total reaction time is 7 hours, thus obtaining the silane modified diallyl bisphenol compound. FIG. 1 is an IR spectrum of a silane-modified diallyl bisphenol compound of example 2. Raw material diallyl bisphenol A is 3422cm -1 There was a strong absorption front of OH groups, but on the IR spectrum of the product this absorption front had disappeared and the product was at 928cm -1 A strong Si-O-Ph-based absorption front is generated, and the successful synthesis of the silane modified diallyl bisphenol compound can be proved by the above.
Example 3
72.3g of diallyl bisphenol A (purity > 90%) is placed in a four-mouth round bottom flask, stirred and heated to 145 ℃, 0.133g of tetra-n-butyl ammonium bromide is added, 58.3g of methyl vinyl dimethoxy silane (XL 12, wacker in Germany) is added dropwise into a reaction tank after being uniformly stirred, the dropwise adding time is 5 hours, methanol liquid generated in the reaction process is collected, and the total reaction time is 8 hours, thus obtaining the silane modified diallyl bisphenol compound.
The raw material formulations and reaction conditions of examples 1 to 3 are summarized in the following table 1:
TABLE 1
In summary, the present invention provides a silane modified diallyl bisphenol compound as a small molecule multifunctional crosslinking agent, which comprises at least two functional groups with crosslinkable double bonds, has a higher boiling point, is thermally stable and has low polarity, and can be used with resins such as polyphenylene ether, polytetrafluoroethylene, hydrocarbon resin, etc., thereby providing a thermosetting resin formulation system for 5G materials.
In addition, the invention provides a preparation method of the silane modified diallyl bisphenol compound, which utilizes diallyl bisphenol compound with double-end hydroxyl groups to react with silane with at least one alkoxy group and at least one functional group with a crosslinkable double bond at a terminal band so as to obtain the silane modified diallyl bisphenol compound with the functional group with the crosslinkable double bond at the terminal band. The reaction can generate stable Si-O bond on the structure of diallyl bisphenol compound, and the Si-O bond has high bond energy, so the reaction has the characteristics of good heat resistance, flame resistance, low water absorption, weather resistance, corrosion resistance and the like; meanwhile, the Si-O bond angle is large, so that the molecule is easy to rotate freely, better in flexibility and capable of providing excellent toughness.
On the other hand, the silane-modified diallyl bisphenol compound of the present invention is introduced with a silane having low polarity and lubricating properties, so that the viscosity of the diallyl bisphenol compound itself can be further reduced, and the operation of the crosslinking agent can be facilitated. The silane modified diallyl bisphenol compound of the invention has at least two reactive double bonds in the structure, can carry out crosslinking reaction with modified polyphenyl ether, further improves the crosslinking density, and forms cured resin with high crosslinking density, so that the silane modified diallyl bisphenol compound can be used on a polyphenyl ether resin series laminated plate, and can also be compounded with bismaleimide resin as a raw material to form a thermosetting resin composition with low shrinkage, high Tg, high heat resistance and low dielectric property.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (6)
1. A process for producing a silane-modified diallyl bisphenol compound, which comprises the steps of:
reaction type (1)
In the reaction formula (1), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R2 is a C1 to C6 alkyl group, R3 is a functional group having a crosslinkable double bond, n+m is a positive integer of 1 to 8, and a is a positive integer of 1 to 4.
2. The method for producing a silane-modified diallyl bisphenol compound as claimed in claim 1, wherein the functional group having a crosslinkable double bond comprises an acryl group, a vinyl group, an acryl group or a methacryl group.
3. The process for producing a silane-modified diallyl bisphenol compound as claimed in claim 1, wherein n+m is 2 or 3.
4. The process for producing a silane-modified diallyl bisphenol compound as claimed in claim 1, wherein the reaction temperature of the reaction formula (1) is 100 to 180 ℃.
5. The method for producing a silane-modified diallyl bisphenol compound as claimed in claim 1, wherein the ratio of the diallyl bisphenol compound to the dialkoxysilane having a functional group having a crosslinkable double bond, calculated as the molar ratio of the hydroxyl groups of the diallyl bisphenol compound to the dialkoxysilane having a functional group having a crosslinkable double bond, is 1:0.5 to 1:4.0.
6. the process for producing a silane-modified diallyl bisphenol compound as claimed in claim 1, wherein the catalyst of the reaction formula (1) is used in an amount of 500ppm to 5000ppm based on the weight of the diallyl bisphenol compound.
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