TW201910359A - Low polarity resin, and preparation method therefor and use thereof - Google Patents

Abstract

The present invention provides a low polarity resin, and a preparation method therefor and the use thereof. The low polarity resin has a structure as shown in formula I and is based on a phenolic compound or resin, and prepared by a three-step reaction of allyl etherification, rearrangement and alkyl etherification. The resin does not contain polar hydroxyl groups in the molecular formula thereof, has a stable molecular structure, low polarity, and high reactivity, and does not generate polar hydroxyl groups during application and processing, thereby avoiding the influence of secondary hydroxyl groups on the performance of products thereof. While the resin improves the dielectric performance, same still has crosslinkable reactive groups which lead to no significant change in high temperature resistance after curing, can be used in one of the components of matrix resins in the resin composite material, and can be co-crosslinked and cured with other thermosetting resins, which significantly reduces the dielectric constant and dielectric loss of the resin. The use of the resin in the preparation of a metal foil clad laminate facilitates reducing the dielectric constant and dielectric loss of the metal foil clad laminate, and results in higher resistance to high temperature, such that the metal foil clad laminate has good comprehensive properties.

Description

 Low polarity resin and preparation method and application thereof  

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

High performance thermosetting resins are widely used in aerospace, rail transit, power insulation, microelectronic packaging due to their excellent heat resistance, flame retardancy, weather resistance, electrical insulation, good mechanical properties and dimensional stability. Resin matrix, high temperature resistant insulation materials and adhesives for composite materials in other fields. Commonly used high-performance thermosetting resins include epoxy resin, phenolic resin, and bismaleimide resin. However, the above-mentioned resin has brittleness, which results in insufficient impact resistance of the material, and the resin has a high molecular structure polarity, resulting in weaknesses such as high dielectric constant and loss. In order to limit its promotion and application in certain fields, research on thermosetting resin modification has always been a research topic of concern to material workers.

In recent years, high-temperature thermosetting resins typified by bismaleimide resins have been increasingly used in aerospace aerospace radomes, rail transit circuit insulation materials and microelectronic circuit boards. With the rapid development of the above-mentioned industries, the electromagnetic transmission power and frequency are increasing, and the requirements for the wave transmission and insulation properties of materials are increasing. The dielectric constants and losses of ordinary high temperature resistant thermosetting resins are too high, and the transmission properties of the transmission are no longer possible. Meet the design requirements of radar, insulation materials and microelectronic circuit boards. Therefore, how to reduce the polarity of the resin and thus the dielectric constant and loss has always been a technical bottleneck concern of researchers.

Synthesizing new structural monomers or resins is a viable method of reducing dielectric constant and loss. CN104311756A discloses a bismuth-containing bismaleimide resin which can reduce the dielectric constant to less than 3.0. CN104479130A discloses a novel bis-maleimide monomer having a fluorine-containing structure, which significantly reduces the dielectric constant and loss of a bismaleimide resin. However, the above-mentioned novel structure of the bismaleimide monomer has a complicated synthesis process and high cost, and is difficult to prepare and apply in batches. In addition, copolymerization modification by other resins is one of the important methods for improving the insulation properties of thermosetting resins. CN101338032A discloses the use of a cyanate-modified bismaleimide resin to prepare a prepreg, and the dielectric constant and loss of the composite material are significantly reduced. However, this method has certain effects on improving the dielectric properties of the resin, but the degree is limited, and there is still a certain gap in the distance application.

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

In view of the deficiencies of the prior art, it is an object of the present invention to provide a low polarity resin and a preparation method and application thereof. The resin of the present invention does not contain a polar group (for example, a hydroxyl group), has low molecular polarity, high reactivity, lowers the dielectric constant and loss of the cured product, and further ensures good mechanical strength and good high temperature resistance of the cured product. .

In order to attain the object of the present invention, the present invention employs the following technical means: In one aspect, the present invention provides a low polarity resin having the structure shown in Formula I below:

Wherein R is a linear or branched alkyl group, , -O-, or X and Y are independently hydrogen, allyl, linear alkyl, branched alkyl, or a combination of at least two, A being a linear or branched alkyl or arylalkyl group, n being An integer from 1-20.

In the low-polarity resin described in the present invention, the aforementioned low polarity means that it does not contain a polar group, and particularly does not contain a hydroxyl group, so that the resin has a low polarity, and overcomes the high frequency of the thermosetting resin. The defects of high electrical constant and high loss can be achieved by cross-linking curing of the allyl structure in the structure to ensure the mechanical strength after curing, and further ensure that the cured product has excellent heat resistance.

Desirably, the aforementioned R is a linear alkyl group of C1-C6 (e.g., C1, C2, C3, C4, C5 or C6) or a C3-C6 (e.g., C3, C4, C5 or C6) branched alkyl group, specifically Can be -CH ₂ -, or Wait.

Ideally, R is -CH ₂ -, , -O-, or And X and Y are independently a hydrogen, an allyl group, a linear alkyl group, a branched alkyl group, or a combination of at least two, and A is a linear or branched alkyl group or an arylalkyl group.

In the present invention, n is an integer of 1-20, 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.

Desirably, X and Y are independently C1-C21 (eg, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, a linear alkyl group of C19, C20 or C21) or C3-C21 (eg C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19) , C20 or C21) branched alkyl.

Desirably, A is C1-C21 (eg, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20 or Linear alkyl or C3-C21 of C21) (eg C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20 or C21) A branched alkyl group may specifically be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or the like.

Desirably, the aforementioned arylalkyl group is a benzyl group, that is,

Desirably, the aforementioned low polarity resin is any one or a combination of at least two of the compounds having the structures of the following formulas A to D: Wherein n is an integer from 1-20.

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

(1) The phenolic compound or the phenolic resin represented by the formula II is reacted with an allylation reagent to obtain an allyl etherified resin of the formula III, and the reaction formula is as follows:

(2) heating the allyl etherified resin of formula III under protective gas protection, and undergoing intramolecular rearrangement reaction to obtain an allylated phenolic resin of formula IV;

(3) an allylated phenolic resin of the formula III is reacted with an alkylating agent to obtain a low polarity resin of the formula I; Wherein R ₁ is a linear or branched alkyl group, , -O-, or ; R ₂ is a linear or branched alkyl group; , -O-, or ; R ₃ is a linear or branched alkyl group; -O-, or ; R is a linear or branched alkyl group, , -O- or or X and Y are independently any one or a combination of at least two of hydrogen, allyl, linear alkyl or branched alkyl; A is a linear or branched alkyl or arylalkyl group, n is An integer from 1-20.

In the present invention, in the rearrangement step of step (2), when R ₂ is or In the case where the allyl ether group is contained therein, rearrangement occurs, resulting in the inclusion of an allyl group due to rearrangement in the intermediate unit R ₃ of the allylated phenolic resin represented by Formula IV, and further in the product formula I The R unit of the low-polarity resin shown contains allyl groups produced by rearrangement. In the present invention, the ally is not directly represented in the corresponding structures of R ₃ and R, but is represented only by X. All substituents on the phenyl ring, however it is clear here that X contains allyl groups due to rearrangement, if R ₂ is before the rearrangement reaction or , the other substituent X is present on the benzene ring, and after the rearrangement reaction of the step (2), the structure of the R ₃ or The middle X may represent a combination of allyl groups produced by rearrangement and other substituents before the reaction. Of course, in the rearrangement step of step (2), R ₂ is also included. or When, R ₂ unit allyl ether group rearrangement reaction does not occur at this time, the reaction product of R ₃ and R before the reaction of X in the allyl ether of formula III in the resin of R ₂ X The groups are the same.

Desirably, the phenolic compound or the phenolic resin described in the step (1) is a phenol, a dihydric phenol, a polyhydric phenol or a derivative thereof, and is preferably phenol, o-cresol, bisphenol A, bisphenol F, and quaternary Any one or a combination of at least two of a bisphenol A, a phenol resin, an o-cresol novolac resin or a cyclopentadiene phenol resin.

Desirably, the aforementioned allylating agent is any one or a combination of at least two of allyl decyl alcohol, allyl chloride, allyl bromide, allyl iodide or allylamine.

Desirably, the molar ratio of the aforementioned phenolic compound or phenolic resin to the allylating agent is 1: (0.3 to 1.2), for example 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.

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

Desirably, the molar ratio of the above-mentioned basic substance to the phenolic hydroxyl group contained in the phenolic compound or the phenolic resin described in the 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.

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

Desirably, the aforementioned phase transfer catalyst is a quaternary ammonium salt phase transfer catalyst, preferably tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctane. Any one or a combination of at least two of methylammonium chloride, dodecyltrimethylammonium chloride or tetradecylbromotrimethylammonium chloride.

Desirably, the amount of the phase transfer catalyst added is 0.1 to 5% by mass of the phenolic compound or the phenolic resin described in the step (1), 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%.

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

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

Desirably, the temperature of the reaction described in the step (1) is 60 to 90 ° C, for example, 60 ° C, 63 ° C, 65 ° C, 68 ° C, 70 ° C, 75 ° C, 78 ° C, 80 ° C, 85 ° C, 88 ° C or 90 ° C.

Desirably, the reaction time described in the step (1) is 4 to 6 hours, for example, 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.

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

Desirably, the heating described in step (2) is heated to 180 to 220 ° C, such as 180 ° C, 185 ° C, 190 ° C, 195 ° C, 200 ° C, 205 ° C, 210 ° C, 215 ° C or 220 ° C.

Desirably, the reaction time described in the step (2) is 4 to 6 hours, for example, 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.

Desirably, the alkylating agent described in the step (3) is a halogenated alkane, preferably methyl chloride, ethyl chloride, chloropropane, chlorobutane, methyl bromide, ethyl bromide, bromopropane, bromobutane, benzyl bromide. Or any one or a combination of at least two of benzyl chloride.

Desirably, the molar ratio of the phenolic hydroxyl group in the allylated phenolic resin of the formula III described in the step (3) to the alkyl group in the alkylating agent is 1: (1 to 1.2), for example 1:1, 1:1.05, 1:1.1, 1:1.15 or 1:1.2. The phenolic hydroxyl groups in the molecular structure of the resin obtained by the reaction are all etherified with an alkyl group, so that the resin has no polar hydroxyl group.

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

Desirably, the aforementioned basic substance is an inorganic base, preferably any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.

Desirably, the molar ratio of the aforementioned basic substance to the phenolic hydroxyl group in the allylated phenolic resin represented by Formula III is (1 to 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.

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

Desirably, the aforementioned phase transfer catalyst is a quaternary ammonium salt phase transfer catalyst, preferably tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctane. Any one or a combination of at least two of methylammonium chloride, dodecyltrimethylammonium chloride or tetradecylbromotrimethylammonium chloride.

Desirably, the amount of the phase transfer catalyst added is 0.1 to 5% by mass of the allylated phenolic resin described in the step (3), 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%.

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

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

Desirably, the temperature of the reaction described in the step (3) is 60 to 90 ° C, for example, 60 ° C, 63 ° C, 65 ° C, 68 ° C, 70 ° C, 75 ° C, 78 ° C, 80 ° C, 85 ° C, 88 ° C or 90 ° C.

Desirably, the reaction time described in the step (3) is 4 to 6 hours, for example, 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 of the invention does not contain polar hydroxyl groups, and has stable molecular structure, low molecular polarity and high reactivity, and does not generate polar hydroxyl groups during the application process, and avoids the generation of The effect of the secondary hydroxyl group on the properties of its product.

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

The low-polarity resin of the present invention can be used for one of the constituent components of the matrix resin in the resin composite material, and can be co-crosslinked and cured with other thermosetting resins such as bismaleimide, and the dielectric constant and dielectric loss of the resin are remarkably lowered.

In the present invention, the resin composite material may be an aerospace wave-transparent composite material, a power insulating material, a resin composite material for electronic packaging, or a resin composite material for a copper-clad laminate.

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

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

In another aspect, the invention provides the use of a low polarity resin as described above in the preparation of a metal foil laminate.

The low-polarity resin described in the present invention can be used for one of the constituent components of the matrix resin in the resin composite material, and can be co-crosslinked and cured with other thermosetting resins such as bismaleimide, and the dielectric constant and dielectric loss of the resin are remarkably lowered. The use thereof in the preparation of the metal foil-clad laminate is advantageous for reducing the dielectric constant and dielectric loss of the metal foil-clad laminate, so that the metal foil-clad laminate has good comprehensive performance.

Compared with the prior art, the present invention has the following effects: the resin of the present invention does not contain a polar hydroxyl group, and has a stable molecular structure, a low molecular polarity and a high reactivity, and is not produced during the application process. The polar hydroxyl group avoids the influence of the generated secondary hydroxyl group on the properties of the product. Therefore, the resin has a crosslinkable reactive group while improving the dielectric properties, so that the high temperature resistance after curing has no significant change, and can be used for the resin. One of the components of the matrix resin in the composite material can be co-crosslinked and cured with other thermosetting resins such as bismaleimide, which significantly reduces the dielectric constant and dielectric loss of the resin, and is used in the preparation of the metal foil-clad laminate. It is beneficial to reduce the dielectric constant and dielectric loss of the metal foil-clad laminate, and has high high temperature resistance, so that the metal foil-clad laminate has good comprehensive performance.

Fig. 1 is an infrared spectrum chart of the low polarity resin prepared in Example 1.

The technical means of the present invention will be further described below by way of specific embodiments. It is to be understood by those of ordinary skill in the art that the following examples are merely to be construed as an understanding of the invention.

Example 1

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

(1) 188 g of acetone was added to a three-necked reaction flask, and 228 g of bisphenol A was added to the reaction flask, and after stirring and dissolved, 106 g of sodium carbonate was added. Further, 153 g of a chloropropene solution was slowly added dropwise, followed by a reaction for 4 hours to stop the reaction. The salt is removed by filtration, most of the solvent is removed, and the residual solvent and water are removed to obtain bisphenol A diallyl ether.

(2) 134 g of bisphenol A diallyl ether prepared in the step 1 was placed in a reaction flask, heated to carry out a rearrangement reaction, and the temperature was discharged to obtain a brown viscous liquid, that is, diallyl bisphenol A.

(3) 402 g of n-butanol was added to the reaction flask, and 154 g of diallyl bisphenol A prepared in the step 2 was placed in a reaction flask, and after stirring and dissolved, 138 g of potassium carbonate was added. 157 g of a chloropropane solution was slowly added dropwise, followed by a temperature rise reaction for 6 hours to stop the reaction. Filtration, removal of most of the solvent, washing, and removal of residual solvent and water, to obtain 3,3'-diallyl-4,4'-dipropylphenoxypropane, the aforementioned low polarity resin, its structure As follows:

The infrared spectrum of 3,3'-diallyl-4,4'-dipropylphenoxypropane prepared in this example is shown in Fig. 1. It can be seen that the hydroxyl group at 3300-3500 cm ^-1 The structure has disappeared and does not contain polar hydroxyl groups, resulting in a significant decrease in molecular polarity.

Example 2

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

(1) 300 g of n-butanol was added to a three-neck reaction flask, and 114 g of a novolak type phenol resin was added to the reaction flask, and after stirring and dissolved, 56 g of potassium hydroxide was added. 153 g of a bromopropene solution was slowly added dropwise, followed by a temperature increase reaction for 4 hours, and then the reaction was stopped. Filtration, washing, and removal of residual solvent and water give an allyl etherified phenolic resin.

(2) 141 g of the allyl etherified phenolic resin prepared in the step 1 was placed in a reaction flask, heated to carry out a rearrangement reaction, and the temperature was discharged to obtain a brown viscous liquid, that is, an allyl phenolic resin.

(3) 402 g of n-butanol was placed in the reaction flask, and 141 g of allyl phenolic resin prepared in the step 2 was placed in a reaction flask, stirred and dissolved, and then 104 g of sodium carbonate was added. 171 g of a chlorobutane solution was slowly added dropwise, followed by a temperature increase reaction for 6 hours, and then the reaction was stopped. Filtration, washing, and removal of the solvent and water to obtain a butyl etherified allyl phenolic resin, that is, the aforementioned low-polar resin, having an Mn of 1080, the structure of which is as follows:

Example 3

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

(1) To a three-necked reaction flask, 250 g of toluene was added, and 118 g of o-cresol novolac resin was added to the reaction flask, and after stirring and dissolved, 100 g of an aqueous sodium hydroxide solution (concentration: 40%) was added, and 1 g of tetrabutylammonium bromide was further added. Further, 153 g of a chloropropene solution was slowly added dropwise, followed by a temperature increase reaction for 4 hours, the reaction was stopped, and the solvent was removed to obtain an allyl etherified o-cresol novolac resin.

(2) 159 g of the allyl etherified o-cresol novolac resin prepared in the step 1 was placed in a reaction flask, and the rearrangement reaction was carried out by heating, and the temperature was discharged to obtain a dark brown semisolid as an allyl o-cresol novolac resin.

(3) 300 g of toluene was added to the reaction flask, and 159 g of the allyl o-cresol novolac resin prepared in the step 2 was placed in a reaction flask, stirred and dissolved, and then 100 g of an aqueous sodium hydroxide solution (40%) was added. After the temperature is constant, 157 g of chloropropane is slowly added dropwise, followed by raising the temperature for 6 hours, then stopping the reaction, washing, and then removing the solvent and water to obtain a propyl etherified allyl o-cresol phenolic resin having an Mn of 1230. The aforementioned low polarity resin has the following structure:

Example 4

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

(1) Add 300 g of xylene to a three-neck reaction flask, add 130 g of cyclopentadiene phenolic resin to the reaction flask, stir and dissolve, add 100 g of sodium hydroxide aqueous solution (concentration: 40%), and add 1 g of tetrabutylammonium bromide. . 153 g of the allyl decyl alcohol solution was slowly added dropwise, followed by a temperature increase reaction for 4 hours, the reaction was stopped, and the solvent was removed to obtain an allyl etherified cyclopentadiene phenol resin.

(2) 141 g of the allyl etherified cyclopentadiene phenolic resin prepared in the step 1 was placed in a reaction flask, heated to carry out a rearrangement reaction, and the temperature was discharged to obtain a dark brown semi-solid as allyl cyclopentadiene phenol Resin.

(3) 300 g of xylene was added to the reaction flask, and 141 g of allylcyclopentadiene phenol resin prepared in the step 2 was placed in a reaction flask, stirred and dissolved, and then 100 g of an aqueous sodium hydroxide solution (40%) was added. After the temperature was constant, 172 g of chlorobutane was slowly added dropwise, followed by a temperature increase reaction for 6 hours, the reaction was stopped, and the solvent and water were removed to obtain a butyl etherified allylcyclopentadiene phenol resin having an Mn of 1450. , that is, the aforementioned low polarity resin, the structure of which is as follows:

Example 5

80 parts by weight of liquid styrene-butadiene resin Ricon 100, 20 parts by weight of phosphorus-containing esterified diallyl bisphenol A prepared in Example 1, 85 parts by weight of cerium oxide (525), and 6.5 parts by weight of initiator DCP Mixing, adjusting to a suitable viscosity with a solvent of toluene, stirring and mixing uniformly, and uniformly dispersing the filler in the resin to obtain a glue. The above glue was impregnated with a 1080 glass cloth, and then the solvent was removed by drying to obtain a prepreg. Eight pre-cured sheets were laminated, and a copper foil of 1 oz (ounce) thickness was pressed on both sides thereof, and solidified in a press for 2 hours at a curing pressure of 50 kg/cm ² and a curing temperature of 190 ° C. A copper clad laminate is obtained.

Example 6

The only difference from the embodiment 5 is that the 3,3'-diallyl-4,4'-dipropylphenoxypropane prepared in Example 1 is replaced by the 3,3'- prepared in the second embodiment. Diallyl-4,4'-dipropylphenoxypropane.

Example 7

The only difference from Example 5 is that the 3,3'-diallyl-4,4'-dipropylphenoxypropane prepared in Example 1 was replaced with the propyl etherified alkene prepared in Example 3. Propyl o-cresol novolac resin.

Example 8

The only difference from Example 5 is that the 3,3'-diallyl-4,4'-dipropylphenoxypropane prepared in Example 1 was replaced with the butyl etherified alkene prepared in Example 4. Propylcyclopentadiene phenolic resin.

Comparative example 1

80 parts by weight of liquid styrene-butadiene resin Ricon 100, 85 parts by weight of cerium oxide (525), 5.8 parts by weight of initiator DCP were mixed, adjusted to a suitable viscosity with a solvent of toluene, stirred and uniformly mixed, and the filler was uniformly dispersed. In the resin, a glue is obtained. The above glue was impregnated with a 1080 glass cloth, and then the solvent was removed by drying to obtain a prepreg. Eight pre-cured sheets were laminated, and a copper foil of 1 oz (ounce) thickness was pressed on both sides thereof, and solidified in a press for 2 hours at a curing pressure of 50 kg/cm ² and a curing temperature of 190 ° C. A copper clad laminate is obtained.

The raw material sources used in Examples 6-10 and Comparative Example 1 are shown in Table 1, and the physical property data of the prepared copper clad laminates are shown in Table 2.

It can be seen from Table 2 that the low polarity intrinsic flame retardant resin prepared by the invention can make the copper clad laminate have lower dielectric constant and dielectric loss, and has better high temperature resistance and flame retardant performance.

The Applicant declares that the present invention describes the low-polarity resin of the present invention and its preparation method and application by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must be implemented by relying on the above embodiments. . It is to be understood by those skilled in the art that any modifications of the invention, the substitution of the materials of the invention, and the addition of the auxiliary components, the selection of the specific means, etc., are within the scope of the invention and the scope of the disclosure.

Claims (30)

A low polarity resin characterized in that the low polarity resin has a structure represented by the following formula I: Wherein R is a linear or branched alkyl group, , -O-, or X and Y are independently hydrogen, allyl, linear alkyl, branched alkyl, or a combination of at least two; A is a linear or branched alkyl or arylalkyl group, n is An integer from 1-20. A low-polarity resin as recited in claim 1, wherein R is -CH2-, , -O-, or n is an integer from 1 to 20, and X and Y are independently any one or a combination of at least two of hydrogen, allyl, linear alkyl or branched alkyl, and A is a linear or branched alkyl group. Or arylalkyl.  The low polarity resin according to claim 2, wherein the arylalkyl group is a benzyl group.   The low-polarity resin according to the second aspect of the invention, wherein the low-polarity resin is any one or a combination of at least two of the compounds having the structures represented by the following formulas A to D: And n is an integer from 1-20. The method for producing a low-polarity resin according to any one of claims 1 to 4, wherein the method comprises the following steps: (1) a phenolic compound or a phenolic resin represented by Formula II, and allylation The reagent is reacted to obtain an allyl etherified resin of the formula III, and the reaction formula is as follows: (2) heating the allyl etherified resin of formula III under protective gas protection, and undergoing intramolecular rearrangement reaction to obtain an allylated phenolic resin of formula IV; (3) an allylated phenolic resin of the formula IV is reacted with an alkylating agent to obtain a low polarity resin of the formula I; Moreover, R1 is a linear or branched alkyl group. , -O-, or ; R ₂ is a linear or branched alkyl group; , -O-, or ; R ₃ is a linear or branched alkyl group; , an O-, or ; R is a linear or branched alkyl group, , -O-, or X and Y are independently hydrogen, allyl, linear alkyl, branched alkyl, or a combination of at least two; A is a linear or branched alkyl or arylalkyl group, n is An integer from 1-20.  The preparation method according to the fifth aspect of the invention, wherein the phenolic compound or the phenolic resin described in the step (1) is a phenol, a dihydric phenol, a polyhydric phenol or a derivative thereof; the allylation reagent Any one or a combination of at least two of allyl decyl alcohol, allyl chloride, allyl bromide, allyl iodide or allylamine; the aforementioned phenolic compound or phenolic resin and allylate The molar ratio of the reagent is 1: (0.3 to 1.2).    The preparation method according to the sixth aspect of the invention, wherein the phenol compound or the phenol resin described in the step (1) is phenol, o-cresol, bisphenol A, bisphenol F, tetramethyl bisphenol A. Any one or a combination of at least two of a phenol resin, an o-cresol novolac resin or a cyclopentadiene phenol resin.    The production method according to the sixth aspect of the invention, wherein the reaction described in the step (1) is carried out in the presence of a basic substance; the basic substance and the phenolic compound or the phenolic resin described in the step (1) The molar ratio of the phenolic hydroxyl group contained in the medium is (0.3 to 1.4): 1.    The preparation method according to the eighth aspect of the invention, wherein the alkaline substance is any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.    The production method according to any one of the items 5 to 9, wherein the reaction described in the step (1) is carried out in the presence of a phase transfer catalyst; and the phase transfer catalyst is added in the amount of the step (1). 0.1 to 5% by mass of the phenolic compound or phenolic resin described.    The production method according to claim 10, wherein the phase transfer catalyst is a quaternary ammonium salt phase transfer catalyst.    The preparation method according to claim 11, wherein the phase transfer catalyst is tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, Any one or a combination of at least two of trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetradecylbromotrimethylammonium chloride.    The preparation method according to claim 10, wherein the solvent of the reaction described in the step (1) is any one or a combination of at least two of an alcohol solvent, an aromatic hydrocarbon solvent or a ketone solvent; The amount added is 2 to 5 times the mass of the phenolic compound or the phenolic resin described in the step (I).    The preparation method according to Item 13, wherein the solvent of the reaction described in the step (1) is any one or a combination of at least two of ethanol, propanol, butanol, toluene or xylene.    The preparation method according to claim 10, wherein the temperature of the reaction described in the step (1) is 60 to 90 ° C; and the reaction time described in the step (1) is 4 to 6 hours.    The preparation method according to any one of claims 5 to 9, wherein the protective gas described in the step (2) is nitrogen or argon; and the heating described in the step (2) is heated to 180~. 220 ° C; the reaction time described in the step (2) is 4 to 6 hours.    The preparation method according to any one of the items 5 to 9, wherein the alkylating agent described in the step (3) is a halogenated alkane; and the allyl group represented by the formula IV in the step (3) The molar ratio of the phenolic hydroxyl group in the phenolic resin to the alkyl group in the alkylating agent is 1: (1 to 1.2).    The preparation method according to Item 17, wherein the alkylating agent described in the step (3) is methyl chloride, ethyl chloride, chloropropane, chlorobutane, methyl bromide, ethyl bromide or bromopropane. Any one or a combination of at least two of bromobutane, benzyl bromide or benzyl chloride.    The production method according to claim 17, wherein the reaction described in the step (3) is carried out in the presence of a basic substance; the basic substance and the phenolic hydroxyl group in the allylated phenolic resin represented by the formula IV The molar ratio is (1~1.4): 1.    The production method according to claim 19, wherein the basic substance is an inorganic base.    The production method according to claim 20, wherein the alkaline substance is any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.    The production method according to claim 17, wherein the reaction described in the step (3) is carried out in the presence of a phase transfer catalyst; and the phase transfer catalyst is added in an amount of the allylation described in the step (3). The quality of the phenolic resin is 0.1 to 5%.    The production method according to claim 22, wherein the phase transfer catalyst is a quaternary ammonium salt phase transfer catalyst.    The preparation method according to claim 23, wherein the phase transfer catalyst is tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, Any one or a combination of at least two of trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetradecylbromotrimethylammonium chloride.    The preparation method according to claim 17, wherein the solvent of the reaction described in the step (3) is any one or a combination of at least two of an alcohol solvent, an aromatic hydrocarbon solvent or a ketone solvent; The amount added is 2 to 5 times the mass of the allylated phenolic resin described in the step (3).    The preparation method according to claim 25, wherein the solvent of the reaction described in the step (3) is any one or a combination of at least two of ethanol, propanol, butanol, toluene or xylene.    The preparation method according to claim 17, wherein the temperature of the reaction described in the step (3) is 60 to 90 ° C; and the reaction time described in the step (3) is 4 to 6 hours.    The use of the low-polarity resin as described in any one of claims 1 to 4 in the preparation of a resin composite material.    The use of a low polarity resin as described in any one of claims 1 to 4 in the preparation of an electronic packaging material.    Use of the low-polarity resin as described in any one of claims 1 to 4 in the preparation of a metal foil-clad laminate.