CN109305894B

CN109305894B - Low-polarity resin and preparation method and application thereof

Info

Publication number: CN109305894B
Application number: CN201710617175.0A
Authority: CN
Inventors: 刘锋; 苏民社
Original assignee: Zhengzhou University; Shengyi Technology Co Ltd
Current assignee: Zhengzhou University; Shengyi Technology Co Ltd
Priority date: 2017-07-26
Filing date: 2017-07-26
Publication date: 2022-07-19
Anticipated expiration: 2037-07-26
Also published as: TW201910359A; CN109305894A; WO2019019481A1; TWI662050B

Abstract

The invention provides a low-polarity resin and a preparation method and application thereof, the low-polarity resin has a structure shown in a formula I, is prepared by three steps of reactions of allyl etherification, rearrangement and alkyl etherification based on phenolic compounds or resins, does not contain polar hydroxyl in molecular formula, has stable molecular structure, low polarity and high reaction activity, does not generate polar hydroxyl in the application and processing process, avoids the influence of secondary hydroxyl on the product performance, improves the dielectric property, still has crosslinkable reaction groups, does not obviously change the high temperature resistance after curing, can be used as one component of matrix resin in a resin composite material, can be co-crosslinked and cured with other thermosetting resins, obviously reduces the dielectric constant and the dielectric loss of the resin, is beneficial to reducing the dielectric constant and the dielectric loss of a metal-clad laminate in the preparation of a metal-clad laminate, and has higher high temperature resistance, so that the metal foil-clad laminated board has good comprehensive performance.

Description

Low-polarity resin and preparation method and application thereof

Technical Field

The invention belongs to the technical field of thermosetting resin, and relates to low-polarity resin and a preparation method and application thereof.

Background

The high-performance thermosetting resin has the characteristics of excellent heat resistance, flame retardance, weather resistance, electric insulation, good mechanical property, good dimensional stability and the like, and is widely applied to resin substrates, high-temperature-resistant insulating materials, adhesives and the like of composite materials in the fields of aerospace, rail transit, electric power insulation, microelectronic packaging and the like. The commonly used high-performance thermosetting resins include epoxy resin, phenolic resin, bismaleimide resin and the like, but the resins have the defects of insufficient impact resistance of materials due to brittleness, high dielectric constant and high loss due to large polarity of a resin molecular structure and the like, so that the popularization and the application of the resins in certain fields are limited, and the research on the modification of the thermosetting resins is a research subject which is always paid attention to by material workers.

In recent years, bismaleimide resins are used as high-temperature resistant thermosetting resins, and are increasingly used in the fields of aerospace radar antenna covers, track traffic circuit insulating materials, microelectronic circuit boards and the like. With the rapid development of the above industries, the electromagnetic emission power and frequency are continuously increased, the requirements on the wave-transmitting and insulating properties of the materials are increasingly improved, and the wave-transmitting and insulating properties of common high-temperature resistant thermosetting resins cannot meet the design requirements of radars, insulating materials and microelectronic circuit boards due to relatively high dielectric constants and losses. Therefore, how to reduce the polarity of the resin, and thus the dielectric constant and the loss, has been a technical bottleneck problem of attention of researchers.

The synthesis of new structural monomers or resins is a viable approach to reduce dielectric constant and loss. CN104311756A discloses a silicon-containing bismaleimide resin, the introduction of which can reduce the dielectric constant below 3.0. CN104479130A discloses a novel bismaleimide monomer containing a fluorine structure, which remarkably reduces the dielectric constant and loss of bismaleimide resin. However, the bismaleimide monomer with the novel structure has complex synthesis process and high cost, and is difficult to prepare and apply in batches. In addition, modification by copolymerization of other resins is one of important methods for improving the insulating properties of thermosetting resins. CN101338032A discloses that the dielectric constant and loss of the composite material are obviously reduced by adopting cyanate ester modified bismaleimide resin to prepare the prepreg. However, although this method has some effect on improving the dielectric properties of the resin, the degree is limited, and there is a gap from the application.

Therefore, in the art, it is desirable to obtain a resin material with low polarity to reduce the dielectric constant and loss of the cured product thereof, while maintaining the excellent performance of the copper clad laminate in other aspects.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a low-polarity resin and a preparation method and application thereof. The resin does not contain polar groups (such as hydroxyl groups), has low molecular polarity and high reactivity, reduces the dielectric constant and loss of a cured product, and can ensure that the cured product has good mechanical strength, high temperature resistance and other properties.

In order to achieve the purpose, the invention adopts the following technical scheme:

in one aspect, the present invention provides a low polarity resin having a structure represented by formula I below:

wherein R is a linear or branched alkyl group,

-O-、

x and Y are independently any one or combination of at least two of hydrogen, allyl, straight chain alkyl and branched chain alkyl, A is straight chain or branched chain alkyl or aryl alkyl, and n is an integer of 1-20.

In the low-polarity resin, the low polarity means that the resin does not contain a polar group, particularly a hydroxyl group, so that the resin has low polarity, the defects of high-frequency dielectric constant and high loss caused by high polarity of general thermosetting resin are overcome, and meanwhile, cross-linking curing can be realized through an allyl structure in the structure, the mechanical strength after curing is ensured, and the cured product can be ensured to have excellent heat resistance.

Preferably, the R is a linear alkyl group of C1-C6 (e.g., C1, C2, C3, C4, C5 or C6) or C63-C6 (e.g. C3, C4, C5 or C6) branched alkyl, in particular-CH₂-、

And so on.

Preferably, R is-CH₂-、

-O-、

X and Y are independently any one or a combination of at least two of hydrogen, allyl, linear alkyl and branched alkyl, and A is linear or branched alkyl or arylalkyl.

In the present invention, n is an integer of 1 to 20, for example, n may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

Preferably, X and Y are independently a C1-C21 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, or C21) straight chain or C3-C21 (e.g., C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, or C21) branched chain alkyl.

Preferably, a is a linear alkyl of C1-C21 (e.g. C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20 or C21) or a linear alkyl of C3-C21 (e.g. C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C49392 19, C20 or C21), which may in particular be methyl, ethyl, propyl, butyl, pentyl, etc.

Preferably, the arylalkyl group is benzyl, i.e.

Preferably, the low polarity resin is any one of or a combination of at least two of compounds having structures represented by the following formulae a to D:

wherein n is an integer of 1 to 20.

In another aspect, the present invention provides a method for preparing the low polarity resin as described above, the method comprising the steps of:

(1) Reacting a phenolic compound or phenolic resin of formula II with an allylating reagent to provide an allylated resin of formula III, an exemplary reaction formula is as follows:

(2) under the protection of protective gas, heating the allylic etherification resin shown in the formula III to carry out intramolecular rearrangement reaction to obtain allylic phenol resin shown in the formula IV;

(3) reacting allylated phenol resin shown in a formula III with an alkylating reagent to obtain low-polarity resin shown in a formula I;

wherein R is₁Is a linear or branched alkyl group,

-O-、

R₂is a linear or branched alkyl group,

-O-、

R₃is a linear or branched alkyl group,

-O-、

r is a straight-chain or branched alkyl group,

-O-or

X and Y are independently any one or a combination of at least two of hydrogen, allyl, straight chain alkyl or branched chain alkyl; a is a straight or branched chain alkyl or arylalkyl group and n is an integer from 1 to 20.

In the present invention, in the rearrangement step of step (2), when R is₂Is composed of

Including those in which the allyl ether group undergoes rearrangement, resulting in the intermediate unit R of the allylated phenolic resin of formula IV₃Contains allyl generated by rearrangement, and further contains allyl generated by rearrangement in the R unit of the low-polarity resin shown in the formula I, and the allyl is not directly expressed to R for the simplicity of expression in the invention ₃And R represents all substituents on the phenyl ring by X alone, however it is clear here that X contains an allyl group which is produced as a result of the rearrangement if R is present before the rearrangement reaction₂Is composed of

With other substituents X on the phenyl ring, after the rearrangement reaction in step (2), then at R₃Structure of (1)

Wherein X may represent a combination of allyl groups produced by the rearrangement and other substituents prior to the reaction. Of course, in the rearrangement step of step (2), R is also included₂Is composed of

When R is₂In the case where the allyl ether group in the unit does not undergo a rearrangement reaction, in this case, R after the reaction₃And X in the product R and R in the allyl etherified resin shown in the formula III before reaction₂The X groups in (A) are the same.

Preferably, the phenolic compound or phenolic resin in step (1) is phenol, dihydric phenol, polyhydric phenol or derivative resin thereof, preferably any one or combination of at least two of phenol, o-cresol, bisphenol a, bisphenol F, tetramethyl bisphenol a, phenolic resin, o-cresol phenolic resin or cyclopentadiene phenolic resin.

Preferably, the allylating agent is any one of allyl silanol, allyl chloride, allyl bromide, allyl iodide, or allyl amine, or a combination of at least two thereof.

Preferably, the molar ratio of the phenolic compound or phenolic resin to the allylation reagent is 1 (0.3-1.2), such as 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, or 1: 1.2.

Preferably, the reaction of step (1) is carried out in the presence of a basic substance, preferably any one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate or a combination of at least two thereof.

Preferably, the molar ratio of the basic substance to the phenolic hydroxyl groups contained in the phenolic compound or phenolic resin in step (1) is (0.3 to 1.4):1, for example, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1 or 1.4: 1.

Preferably, the reaction of step (1) is carried out in the presence of a phase transfer catalyst.

Preferably, the phase transfer catalyst is a quaternary ammonium salt type phase transfer catalyst, preferably one or a combination of at least two of tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetradecylbromyltrimethylammonium chloride.

Preferably, the phase transfer catalyst is added in an amount of 0.1 to 5% by mass, for example 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8% or 5% by mass of the phenolic compound or phenolic resin of step (1).

Preferably, the solvent for the reaction in step (1) is any one or a combination of at least two of an alcohol solvent, an aromatic hydrocarbon solvent or a ketone solvent, preferably any one or a combination of at least two of ethanol, propanol, butanol, toluene or xylene.

Preferably, the amount of the solvent added is 2 to 5 times, for example 2 times, 2.3 times, 2.5 times, 2.8 times, 3 times, 3.3 times, 3.5 times, 3.8 times, 4 times, 4.3 times, 4.5 times, 4.8 times or 5 times the mass of the phenolic compound or the phenolic resin in step (1).

Preferably, the temperature of the reaction in step (1) is 60-90 ℃, such as 60 ℃, 63 ℃, 65 ℃, 68 ℃, 70 ℃, 75 ℃, 78 ℃, 80 ℃, 85 ℃, 88 ℃ or 90 ℃.

Preferably, the reaction of step (1) is carried out for a period of 4 to 6 hours, such as 4 hours, 4.3 hours, 4.5 hours, 4.8 hours, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.

Preferably, the protective gas in step (2) is nitrogen or argon.

Preferably, the heating in step (2) is carried out to 180-220 ℃, such as 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃ or 220 ℃.

Preferably, the reaction time in step (2) is 4 to 6 hours, such as 4 hours, 4.3 hours, 4.5 hours, 4.8 hours, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.

Preferably, the alkylating agent in step (3) is a halogenated alkane, preferably any one of methyl chloride, ethyl chloride, propyl chloride, butyl chloride, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, benzyl bromide or benzyl chloride or a combination of at least two of them.

Preferably, the molar ratio of the phenolic hydroxyl group in the allylated phenolic resin of formula III in step (3) to the alkyl group in the alkylating reagent is 1 (1-1.2), such as 1:1, 1:1.05, 1:1.1, 1:1.15 or 1: 1.2. Phenolic hydroxyl groups in the molecular structure of the resin obtained by the reaction are etherified by alkyl, so that polar hydroxyl groups are absent in the resin.

Preferably, the reaction of step (3) is carried out in the presence of a basic substance.

Preferably, the alkaline substance is an inorganic base, preferably any one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate or a combination of at least two thereof.

Preferably, the molar ratio of the basic substance to the phenolic hydroxyl groups in the allylated phenolic resin of formula III is (1-1.4): 1, for example 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1 or 1.4: 1.

Preferably, the reaction of step (3) is carried out in the presence of a phase transfer catalyst.

Preferably, the phase transfer catalyst is added in an amount of 0.1 to 5% by mass, e.g. 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8% or 5% by mass of the allylated phenolic resin of step (3).

Preferably, the solvent for the reaction in step (3) is any one or a combination of at least two of an alcohol solvent, an aromatic hydrocarbon solvent or a ketone solvent, preferably any one or a combination of at least two of ethanol, propanol, butanol, toluene or xylene.

Preferably, the solvent is added in an amount of 2 to 5 times, for example 2 times, 2.3 times, 2.5 times, 2.8 times, 3 times, 3.3 times, 3.5 times, 3.8 times, 4 times, 4.3 times, 4.5 times, 4.8 times or 5 times the mass of the allylated phenolic resin of step (3).

Preferably, the temperature of the reaction in step (3) is 60-90 ℃, such as 60 ℃, 63 ℃, 65 ℃, 68 ℃, 70 ℃, 75 ℃, 78 ℃, 80 ℃, 85 ℃, 88 ℃ or 90 ℃.

Preferably, the reaction time in step (3) is 4 to 6 hours, such as 4 hours, 4.3 hours, 4.5 hours, 4.8 hours, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.

The resin prepared by the method does not contain polar hydroxyl, has a stable molecular structure, has the characteristics of low molecular polarity and high reaction activity, does not generate polar hydroxyl in the application processing process, and avoids the influence of generated secondary hydroxyl on the performance of the product.

In another aspect, the present invention provides the use of a low polarity resin as described above in the preparation of a resin composite.

The low-polarity resin can be used as one of the components of matrix resin in a resin composite material, can be co-crosslinked and cured with other thermosetting resins such as bismaleimide and the like, and obviously reduces the dielectric constant and dielectric loss of the resin.

In the invention, the resin composite material can be an aerospace wave-transparent composite material, an electric insulating material, a resin composite material for electronic packaging, a resin composite material for a copper-clad plate and the like.

In another aspect, the present invention provides the use of a low polarity resin as described above in the preparation of an electronic packaging material.

The low-polarity resin disclosed by the invention has the characteristics of low molecular polarity and high reaction activity, and can be applied to the preparation of materials such as electronic packaging adhesives and potting resins.

In another aspect, the present invention provides the use of a low polarity resin as described above in the manufacture of a metal-clad laminate.

The low-polarity resin can be used as one component of matrix resin in a resin composite material, can be co-crosslinked and cured with other thermosetting resins such as bismaleimide and the like, obviously reduces the dielectric constant and dielectric loss of the resin, and is favorable for reducing the dielectric constant and dielectric loss of a metal-clad laminated plate when being used for preparing the metal-clad laminated plate, so that the metal-clad laminated plate has good comprehensive performance.

Compared with the prior art, the invention has the following beneficial effects:

the resin does not contain polar hydroxyl, has a stable molecular structure, has the characteristics of low molecular polarity and high reactivity, does not generate polar hydroxyl in the application processing process, and avoids the influence of generated secondary hydroxyl on the performance of the product, so the resin still has crosslinkable reaction groups while improving the dielectric performance, the high-temperature resistance after curing has no obvious change, can be used as one of the components of matrix resin in a resin composite material, can be subjected to co-crosslinking curing with other thermosetting resins such as bismaleimide and the like, and obviously reduces the dielectric constant and the dielectric loss of the resin.

Drawings

FIG. 1 is an infrared spectrum of a low polarity resin prepared in example 1.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Example 1

In this example, a low polarity resin was prepared by the following method, including the steps of:

(1) 188g of acetone was added into a three-neck reaction flask, 228g of bisphenol A was added into the reaction flask, and after stirring and dissolving, 106g of sodium carbonate was added. 153g of chloropropene solution was slowly added dropwise, and the reaction was stopped after 4 hours. Filtering to remove salt, removing most of the solvent, washing, and removing residual solvent and water to obtain the bisphenol A diallyl ether.

(2) And (2) putting 134g of bisphenol A diallyl ether prepared in the step (1) into a reaction bottle, heating for rearrangement reaction, cooling and discharging to obtain brown viscous liquid, namely diallyl bisphenol A.

(3) 402g of n-butanol was added to a reaction flask, 154g of the diallylbisphenol A prepared in step 2 was put into the reaction flask, and after stirring and dissolving, 138g of potassium carbonate was added. 157g of chloropropane solution is slowly added dropwise, and then the temperature is increased for reaction for 6 hours, and the reaction is stopped. Filtering, removing most of the solvent, washing, and removing residual solvent and water to obtain the 3,3 '-diallyl-4, 4' -dipropylphenoxypropane, namely the low-polarity resin, which has the following structure:

The infrared spectrum of 3,3 '-diallyl-4, 4' -dipropylphenoxypropane prepared in this example is shown in FIG. 1, and 3300-^-1The hydroxyl structure of the (A) has disappeared, and the (A) does not contain polar hydroxyl groups, so that the polarity of the molecule is obviously reduced.

Example 2

(1) 300g of n-butanol was added to a three-neck reaction flask, 114g of novolac resin was added to the reaction flask, and 56g of potassium hydroxide was added after stirring and dissolution. 153g of a bromopropene solution was slowly added dropwise, and the reaction was stopped after 4 hours of reaction at an elevated temperature. Filtering, washing, and removing residual solvent and water to obtain the allyl etherified phenolic resin.

(2) And (2) putting 141g of the allyl etherified phenolic resin prepared in the step (1) into a reaction bottle, heating for rearrangement reaction, cooling and discharging to obtain brown viscous liquid, namely the allyl phenolic resin.

(3) 402g of n-butanol was added to the reaction flask, 141g of the allylphenol-formaldehyde resin prepared in step 2 was placed in the reaction flask, and after stirring and dissolving, 104g of sodium carbonate was added. 171g of chlorobutane solution was slowly added dropwise, and then the reaction was stopped after the reaction was allowed to warm for 6 hours. Filtering, washing, and removing the solvent and water to obtain the butyl etherified allyl phenolic resin, namely the low-polarity resin, wherein the Mn of the resin is 1080 and the structure of the resin is as follows:

Example 3

(1) 250g of toluene was added to a three-neck reaction flask, 118g of o-cresol novolac resin was added to the reaction flask, and after stirring and dissolution, 100g of an aqueous sodium hydroxide solution (concentration: 40%) was added, and 1g of tetrabutylammonium bromide was added. And slowly dropwise adding 153g of chloropropene solution, heating to react for 4 hours, stopping the reaction, washing, and removing the solvent to obtain the allyl etherified o-cresol novolac resin.

(2) And (2) putting 159g of the allyl etherified o-cresol novolac resin prepared in the step (1) into a reaction bottle, heating for rearrangement reaction, cooling and discharging to obtain the dark brown semisolid allyl o-cresol novolac resin.

(3) 300g of toluene was charged into a reaction flask, 159g of the allylo-cresol novolac resin prepared in step 2 was placed in the reaction flask, and after dissolving the resin by stirring, 100g of an aqueous sodium hydroxide solution (40%) was added. After the temperature is constant, slowly adding 157g of chloropropane dropwise, heating to react for 6 hours, stopping the reaction, washing, and removing the solvent and water to obtain the propyl etherified allyl o-cresol novolac resin, wherein the Mn is 1230, namely the low-polarity resin has the following structure:

Example 4

In this example, a low polarity resin was prepared by the following method, comprising the steps of:

(1) 300g of xylene is added into a three-mouth reaction bottle, 130g of cyclopentadiene phenolic resin is added into the reaction bottle, after stirring and dissolving, 100g of sodium hydroxide aqueous solution (with the concentration of 40 percent) is added, and 1g of tetrabutylammonium bromide is added. And slowly dripping 153g of allyl silanol solution, heating to react for 4 hours, stopping the reaction, washing, and removing the solvent to obtain the allyl etherified cyclopentadiene phenolic resin.

(2) And (2) putting 141g of the allyl etherified cyclopentadiene phenolic resin prepared in the step (1) into a reaction bottle, heating for rearrangement reaction, cooling and discharging to obtain the deep brown semisolid allyl cyclopentadiene phenolic resin.

(3) 300g of xylene was charged into a reaction flask, 141g of the allylcyclopentadiene phenolic resin prepared in step 2 was put into the reaction flask, and after dissolving by stirring, 100g of an aqueous sodium hydroxide solution (40%) was added. After the temperature is constant, slowly dropwise adding 172g of chlorobutane, heating to react for 6 hours, stopping the reaction, washing, and removing the solvent and water to obtain the butyl etherified allyl cyclopentadiene phenolic resin, wherein Mn is 1450, namely the low-polarity resin has the following structure:

Example 5

80 parts by weight of liquid styrene-butadiene resin Ricon100, 20 parts by weight of phosphorus-containing esterified diallyl bisphenol A prepared in example 1, 85 parts by weight of silica (525) and 6.5 parts by weight of initiator DCP are mixed, solvent toluene is used for adjusting the viscosity to be proper, the mixture is stirred and mixed uniformly, and the filler is uniformly dispersed in the resin to prepare glue solution. And (3) dipping the glue solution by 1080 glass fiber cloth, and then drying to remove the solvent to obtain the prepreg. Eight sheets of the prepared prepregs were stacked, copper foils of 1oz thickness were laminated on both sides thereof, and cured in a press for 2 hours at a curing pressure of 50Kg/cm²And the curing temperature is 190 ℃, so that the copper-clad plate is obtained.

Example 6

The only difference from example 5 is that 3,3 '-diallyl-4, 4' -dipropylphenoxypropane prepared in example 1 was replaced by 3,3 '-diallyl-4, 4' -dipropylphenoxypropane prepared in example 2.

Example 7

The only difference from example 5 is that 3,3 '-diallyl-4, 4' -dipropylphenoxypropane prepared in example 1 is replaced by propyl etherified allyl ortho-cresol novolac resin prepared in example 3.

Example 8

The only difference from example 5 is that 3,3 '-diallyl-4, 4' -dipropylphenoxypropane prepared in example 1 is replaced by a butyl-etherified allyl cyclopentadiene phenolic resin prepared in example 4.

Comparative example 1

Mixing 80 parts by weight of liquid styrene-butadiene resin Ricon100, 85 parts by weight of silicon dioxide (525) and 5.8 parts by weight of initiator DCP, adjusting the mixture to proper viscosity by using solvent toluene, stirring and mixing uniformly to uniformly disperse the filler in the resin to prepare the glue solution. And (3) dipping the glue solution by 1080 glass fiber cloth, and then drying to remove the solvent to obtain the prepreg. Eight sheets of the prepared prepregs were stacked, copper foils of 1oz thickness were laminated on both sides thereof, and cured in a press for 2 hours at a curing pressure of 50Kg/cm²And the curing temperature is 190 ℃, so that the copper-clad plate is obtained.

The raw material sources applied in examples 6 to 10 and comparative example 1 are shown in table 1, and the physical property data of the prepared copper-clad plate is shown in table 2.

TABLE 1

TABLE 2

As shown in Table 2, the low-polarity intrinsic flame-retardant resin prepared by the invention can enable the copper-clad plate to have lower dielectric constant and dielectric loss, and better high-temperature resistance and flame retardance.

The applicant states that the present invention is illustrated by the above examples of the low polarity resin of the present invention and the preparation method and application thereof, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must be implemented by the above examples. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims

1. A low-polarity resin, characterized in that the low-polarity resin is any one of compounds having a structure represented by the following formula B-formula D or a combination of at least two of the compounds:

wherein n is an integer of 1 to 20.

2. The method for producing a low polarity resin according to claim 1, wherein the production method is method B, method C or method D:

the low-polarity resin has a structure shown in a formula B, and the preparation method is a method B which comprises the following steps:

(B1) reacting the phenolic compound or the phenolic resin shown in the formula B-II with an allylation reagent to obtain the allylic etherified resin shown in the formula B-III, wherein the reaction formula is as follows:

(B2) under the protection of protective gas, heating the allylic etherified resin shown in the formula B-III to carry out intramolecular rearrangement reaction to obtain allylic phenolic resin shown in the formula B-IV;

(B3) reacting the allylated phenol resin shown in the formula B-IV with an alkylating reagent to obtain a low-polarity resin shown in the formula B;

in the method B, n is an integer of 1 to 20;

the allylating reagent in step (B1) is any one or a combination of at least two of allyl silanol, allyl chloride, allyl bromide, allyl iodide, or allyl amine;

The alkylating agent in the step (B3) is chlorobutane and/or bromobutane, and A is n-butyl;

the low-polarity resin has a structure shown in formula C, and the preparation method is a method C, and the method C comprises the following steps:

(C1) reacting the phenolic compound or the phenolic resin shown in the formula C-II with an allylation reagent to obtain the allylic etherified resin shown in the formula C-III, wherein the reaction formula is as follows:

(C2) under the protection of protective gas, heating the allylic etherified resin shown in the formula C-III to carry out intramolecular rearrangement reaction to obtain allylic phenolic resin shown in the formula C-IV;

(C3) reacting the allylated phenol resin shown in the formula C-IV with an alkylating reagent to obtain a low-polarity resin shown in the formula C;

in the method C, n is an integer of 1 to 20;

the allylating reagent in step (C1) is any one or a combination of at least two of allyl silanol, allyl chloride, allyl bromide, allyl iodide, or allyl amine;

the alkylating agent of step (C3) is chloropropane and/or bromopropane, a is n-propyl;

the low-polarity resin has a structure shown in a formula D, and the preparation method is a method D, and the method D comprises the following steps:

(D1) reacting the phenolic compound or the phenolic resin shown in the formula D-II with an allylation reagent to obtain the allylic etherified resin shown in the formula D-III, wherein the reaction formula is as follows:

(D2) Under the protection of protective gas, heating the allylic etherification resin shown in the formula D-III to carry out intramolecular rearrangement reaction to obtain allylic phenol resin shown in the formula D-IV;

(D3) reacting the allylated phenol resin shown in the formula D-IV with an alkylating reagent to obtain low-polarity resin shown in the formula D;

in the process D, R₁Is composed of

R₂Is composed of

R₃Is composed of

R is

X is allyl; a is n-butyl, n is an integer of 1-20;

step (D1) the allylating reagent is any one or a combination of at least two of allylsilanol, allylchloride, allylbromide, allyliodide, or allylamine;

the alkylating agent of step (D3) is chlorobutane and/or bromobutane.

3. The process according to claim 2, wherein the molar ratio of the phenolic compound or phenolic resin to the allylating agent in the step (B1), the step (C1) and the step (D1) is 1 (0.3 to 1.2), respectively.

4. The method according to claim 2, wherein the reaction in step (B1), step (C1) and step (D1) is carried out in the presence of a basic substance.

5. The method according to claim 4, wherein the alkaline substance is any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

6. The method according to claim 4, wherein the molar ratio of the basic substance to the phenolic hydroxyl group contained in the phenolic compound or the phenolic resin is (0.3 to 1.4): 1.

7. The method of claim 2, wherein the reaction of step (B1), step (C1) and step (D1) is carried out in the presence of a phase transfer catalyst.

8. The method according to claim 7, wherein the phase transfer catalyst is a quaternary ammonium salt type phase transfer catalyst.

9. The method according to claim 8, wherein the phase transfer catalyst is any one or a combination of at least two of tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, or tetradecylbromyltrimethylammonium chloride.

10. The process according to claim 7, wherein the phase transfer catalyst is added in an amount of 0.1 to 5% by mass based on the mass of the phenolic compound or the phenolic resin.

11. The method according to claim 2, wherein the solvent for the reaction in step (B1), step (C1) and step (D1) is independently any one or a combination of at least two of an alcohol solvent, an aromatic hydrocarbon solvent and a ketone solvent.

12. The method of claim 11, wherein the solvent for the reaction of step (B1), step (C1) and step (D1) is independently any one of ethanol, propanol, butanol, toluene or xylene or a combination of at least two thereof.

13. The method according to claim 11, wherein the amount of the solvent added is 2 to 5 times the mass of the phenolic compound or phenolic resin.

14. The method of claim 2, wherein the reaction temperature of step (B1), step (C1), and step (D1) is 60-90 ℃ independently of each other.

15. The method of claim 2, wherein the reaction time of step (B1), step (C1) and step (D1) is 4-6 hours.

16. The method of claim 2, wherein the protective gas of step (B2), step (C2), and step (D2) is nitrogen or argon.

17. The method as claimed in claim 2, wherein the heating in the step (B2), the step (C2) and the step (D2) is independently at least 180-220 ℃.

18. The method of claim 2, wherein the reaction time of step (B2), step (C2) and step (D2) is 4 to 6 hours.

19. The method according to claim 2, wherein the molar ratio of the phenolic hydroxyl group in the allylated phenolic resin to the alkyl group in the alkylating agent in the step (B3), the step (C3) and the step (D3) is 1 (1-1.2) independently.

20. The method according to claim 2, wherein the reaction of step (B3), step (C3) and step (D3) is carried out in the presence of a basic substance.

21. The method according to claim 20, wherein the basic substance is an inorganic base.

22. The method of claim 21, wherein the alkaline substance is any one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate or a combination of at least two of them.

23. The method according to claim 21, wherein the molar ratio of the basic substance to the phenolic hydroxyl group in the allylated phenol resin is (1-1.4): 1.

24. The method according to claim 2, wherein the reaction of step (B3), step (C3) and step (D3) is carried out in the presence of a phase transfer catalyst.

25. The method of claim 24, wherein the phase transfer catalyst is a quaternary ammonium salt type phase transfer catalyst.

26. The method of claim 25, wherein the phase transfer catalyst is any one or a combination of at least two of tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, or tetradecylbromyltrimethylammonium chloride.

27. The process of claim 24, wherein the phase transfer catalyst is added in an amount of 0.1 to 5% by mass of the allylated phenolic resin.

28. The method according to claim 2, wherein the solvent for the reaction in step (B3), step (C3) and step (D3) is any one or a combination of at least two of an alcohol solvent, an aromatic hydrocarbon solvent and a ketone solvent.

29. The method of claim 28, wherein the solvent for the reaction of step (B3), step (C3) and step (D3) is any one or a combination of at least two of ethanol, propanol, butanol, toluene or xylene.

30. The method according to claim 28, wherein the solvent is added in an amount of 2 to 5 times the mass of the allylated phenol resin.

31. The method of claim 2, wherein the reaction temperature of step (B3), step (C3), and step (D3) is 60-90 ℃ independently of each other.

32. The method of claim 2, wherein the reaction time of step (B3), step (C3) and step (D3) is 4-6 hours.

33. Use of the low polarity resin of claim 1 in the preparation of a resin composite.

34. Use of the low polarity resin according to claim 1 in the preparation of electronic packaging materials.

35. Use of a low polarity resin according to claim 1 in the manufacture of a metal foil clad laminate.