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CN107325277A - Polyphenylene oxide resin and its application - Google Patents

Polyphenylene oxide resin and its application Download PDF

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Publication number
CN107325277A
CN107325277A CN201610272675.0A CN201610272675A CN107325277A CN 107325277 A CN107325277 A CN 107325277A CN 201610272675 A CN201610272675 A CN 201610272675A CN 107325277 A CN107325277 A CN 107325277A
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polyphenylene ether
formula
ether resin
resin
hours
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CN107325277B (en
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黄达
王宇
谭玉东
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JIANGSU HECHENG NEW MATERIALS Co Ltd
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JIANGSU HECHENG NEW MATERIALS Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C08G65/485—Polyphenylene oxides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/04—End-capping

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention provides the epoxy-capped polyphenylene oxide resin with logical structure shown in formula I, the benzocyclobutene with the structure of formula II end-blocking polyphenylene oxide resin, and the polyphenylene oxide resin comprising logical structure shown in formula I and the structure of formula II composition.Polyphenylene oxide resin and composition disclosed in this invention have that low-k and dielectric loss, water absorption rate are low, shrinkage factor is low, to the substrate adhesion performance such as enough.

Description

Polyphenylene ether resin and use thereof
Technical Field
The invention relates to a polyphenyl ether resin, a semi-cured film containing the polyphenyl ether resin and application of the semi-cured film in the field of copper clad plates.
Background
The Copper Clad Laminate (CCL) is an important plate of a Printed Circuit Board (PCB), and along with the development of the PCB industry to the directions of high transmission speed, light and thin body, the demand on the CCL is higher and higher, and the demand on the high-frequency CCL is very vigorous.
Polyphenylene Ether (PPE) is a thermoplastic engineering plastic with excellent performance and has the following advantages:
(1) excellent physical and mechanical properties. The density is small, the non-toxic, the mechanical strength is high, and the molding shrinkage rate is low;
(2) excellent heat resistance. The glass transition temperature (Tg) is highest in thermoplastic plastics, about 210 ℃, the crystallinity is about 50 percent, the melting point is about 260 ℃, the high-temperature creep-resistant plastic can continuously work within the range of 160-190 ℃, and the creep resistance at high temperature is excellent in thermoplastic engineering plastics;
(3) excellent electrical properties. The PPE molecule structure has no strong polar group, and has stable electrical property and can maintain good electrical property in wide temperature and frequency range. The dielectric constant and the dielectric loss tangent of the composite material are the minimum in engineering plastics and are hardly influenced by temperature, humidity and frequency;
(4) is difficult to burn and has self-extinguishing property. The oxygen index is 29%, and the flame retardance is good;
(5) excellent acid and alkali resistance, stress relaxation resistance and fatigue resistance, and good dimensional stability.
Despite the above series of advantages, PPE as a thermoplastic engineering material has the disadvantages of solvent resistance and fluidity, thereby limiting the popularization and application of PPE in the field of copper clad plates.
Although physical blending can greatly improve the characteristics of the product, the premise of physical blending is that a resin with sufficient excellent performance is required to be selected. The term "sufficiently excellent" as used herein means not only electrical and thermal properties but also solubility of the resin in a solvent for copper clad laminate and compatibility between the resins. Therefore, development and production of resins with reliable performance are of great importance.
In order to fully utilize the excellent dielectric properties and heat resistance of PPE, thermosetting PPE has been first introduced by the Asahi Kasei Pharma industry (JP11012456, 1999-01-19). The thermosetting PPE has allyl radical introduced to the molecular main chain for crosslinking reaction. The Tg of the cured product can be increased to over 240 ℃, and the cured product is insoluble in halogenated hydrocarbon and aromatic hydrocarbon solvents. However, the preparation method of lithium butyl is harsh and has a high risk factor.
The modified polyphenylene ether having terminal allyl groups is obtained by reacting terminal hydroxyl groups with allyl groups, but has a high curing temperature and a large shrinkage due to the allyl activity. The introduction of bismaleimide modified allyl end-capped polyphenylene oxide overcomes the defects of higher hardening temperature and larger shrinkage, but increases reaction steps, increases the complexity of product technology and further influences the stability of products.
The curing temperature of polyphenylene ethers capped with acrylate groups is suitable, but the adhesion of acrylate-modified polyphenylene ethers to substrates is insufficient.
Therefore, there is a particular need for polyphenylene ether resins that combine low dielectric constant and dielectric loss, low water absorption, low shrinkage, and adequate adhesion to the substrate.
Disclosure of Invention
The invention aims to provide an epoxy-terminated modified polyphenylene ether resin which has low dielectric constant and dielectric loss, low water absorption and low shrinkage and has sufficient adhesion to a substrate.
Another object of the present invention is to provide a benzocyclobutene-terminated modified polyphenylene ether resin having a low dielectric constant and dielectric loss, a low water absorption rate, and a low shrinkage rate.
It is another object of the present invention to provide a composition comprising the epoxy-terminated modified polyphenylene ether resin.
It is another object of the present invention to provide a composition comprising the benzocyclobutene-terminated modified polyphenylene ether resin.
It is another object of the present invention to provide a composition comprising both the benzocyclobutene-terminated and epoxy-terminated modified polyphenylene ether resins.
Another object of the present invention is to provide applications of the benzocyclobutene-terminated, epoxy-terminated modified polyphenylene ether resin and the composition thereof.
In order to accomplish the above object of the invention, the present invention provides an epoxy-terminated modified polyphenylene ether resin having a structure of the general formula I:
wherein,
said Z represents an aromatic diphenol structure selected from the group consisting of:
the R is31And R32The same or different, each independently represents hydrogen or methyl;
me represents a methyl group, Et represents an ethyl group;
p, q, r, s, t, u and v are the same or different and each independently represents 0, 1 or 2;
and a and b are the same or different and each independently represent an integer of 0 to 100, wherein m + n represents a positive integer of 1 to 100.
In some embodiments, preferably, Z represents an aromatic diphenol structure selected from the group consisting of:
in some embodiments, preferably, Z represents an aromatic diphenol structure selected from the group consisting of:
in some embodiments of the invention, the general formula i is selected from the following structures:
and
in some embodiments, the general formula i is selected from the following structures:
and
in some embodiments, the general formula i is selected from the following structures:
the inventors found that epoxy-terminated polyphenylene ether resin compounds are relatively widely reported due to the large amount of epoxy resins used in the field of copper clad laminates. In formula I, at least one substituent group Z is disclosed: bisphenol A, tetramethyl bisphenol A, hexafluoro bisphenol A, biphenol and hydroquinone. However, the prior documents and patents only list the synthesis of some bisphenol raw materials, and only remain the first understanding that different bisphenol raw materials have different properties, and no deep understanding is made as to why different bisphenol raw materials are different.
In fact, in the history of synthesis and preparation of high molecular polyphenylene ethers, early studies have focused on how to polymerize small molecular phenols to give methyl-free polyphenylene ether structures, and it has been found that linear methyl-free polyphenylene ether structures with a certain regularity cannot always be obtained by oxidative polymerization of small molecular phenols in any attempt. And a linear polyphenylene oxide structure with certain regularity can be obtained by oxidizing small-molecular 2, 6-dimethylphenol under a proper catalytic system. Two methyl groups of the molecular side chain protect a relatively fragile carbon-oxygen bond in a polyphenyl ether system, and simultaneously, the reaction activity of a benzene ring system is passivated, so that the synthesis is carried out, and the obtained polyphenyl ether with the methyl groups has relatively high heat-resistant and chemical-resistant stability compared with other materials. Therefore, in the polyphenylene ether system, whether the molecular side chain contains methyl or not plays an important role in the preparation of materials and the processing performance.
Based on the above knowledge, since methyl has a significant influence on the synthesis of high molecular polyphenylene ether, it can be reasonably inferred that in the degradation method provided by the present invention, when degrading the existing high molecular polyphenylene ether into oligomeric polyphenylene ether with relatively small molecular weight, whether bisphenol used for degradation has methyl or not will also have a significant influence on the obtained product. After all, the degradation method provided by the invention is a side reaction of synthesizing macromolecular polyphenyl ether by using micromolecules originally.
The methyl group of bisphenol monomer is an important factor influencing reaction and performance, and is not significantly referred to in the process of modifying polyphenylene ether, and the reason for missing the information is that the molecular structures of different bisphenol monomers are quite different, thereby transferring the attention of researchers. In fact, some specific bisphenol monomers do not have methyl, the prepared modified polyphenylene ether also has good effect, and the reason of the seemingly contradictory phenomenon is caused because the influence of the whole framework structure of the bisphenol monomer is larger than the influence of the existence of the methyl, and meanwhile, in the copper-clad plate industry, other components can influence the test result according to different experimental formulas. Therefore, comparison of differences in methyl pair properties under the same formula has only significant meaning under the same framework structure.
From the experiment, we also verify the above deduction, when bisphenol A and tetramethyl bisphenol A are respectively adopted to degrade high molecular weight polyphenyl ether, and the same reagent and synthesis method are adopted to prepare bisphenol A and tetramethyl bisphenol A modified polyphenyl ether, the characteristics of the plate are tested under the same condition, and the comprehensive performance of the tetramethyl bisphenol A modified polyphenyl ether is obviously superior to that of the bisphenol A modified polyphenyl ether system.
Therefore, the epoxy-terminated polyphenylene ether resin of the present invention is more preferably a modified polyphenylene ether containing a methyl bisphenol monomer.
The modified polyphenylene ether resin of the general formula I can be prepared by the following method:
step 1, dissolving high molecular weight polyphenyl ether into a good solvent, adding an initiator and a corresponding bisphenol monomer, stirring and reacting for a plurality of hours at a certain temperature, and adding a poor solvent to precipitate a solid.
The good solvent can be selected from toluene, butanone and cyclohexanone. Toluene is preferred.
The initiator can be selected from conventional initiators such as AIBN (azobisisobutyronitrile) and BPO (benzoyl peroxide). Preferably BPO.
The temperature range is 40-160 ℃. Preferably 110 deg.C
The reaction time is 0.5-24 hours. Preferably 6 hours.
And 2, dissolving the precipitated solid, epoxy chloropropane and a phase transfer catalyst in a solvent in sequence, heating for reaction for a plurality of hours, dropwise adding an alkali solution, reacting for a plurality of hours, cooling, removing the organic solvent, dissolving the solid with acetone, filtering insoluble substances, and adding methanol into the filtrate to precipitate a target product.
The solvent may be any conventional solvent as long as it can dissolve the product. Preferably isopropanol and ethanol.
The phase transfer catalyst is quaternary ammonium salt catalyst, preferably benzyltriethylammonium chloride and tetrabutylammonium chloride.
The temperature range is 40-80 deg.C, preferably 60 deg.C.
The alkali solution is NaOH or KOH aqueous solution, the concentration is 5% -15%, and NaOH aqueous solution with 10% is preferred.
The temperature range is 80-160 ℃. Preferably 110 deg.c.
The reaction time is 2-24 hours. Preferably 2 hours.
The invention provides a benzocyclobutene-terminated modified polyphenyl ether resin with a structure shown in a general formula II:
wherein,
x represents an aromatic diphenol structure;
the m and the n are the same or different and respectively and independently represent an integer of 0-100, wherein m + n represents 0 or a positive integer of 1-100.
In some embodiments of the invention, X is selected from the following structures:
wherein,
R1-R12the same or different, each independently represent a hydrogen, methyl, ethyl and halogen atom; z represents-S-, -SO2-, -SO-, carbonyl, ester group; r21、R22、R23And R24The same or different, each independently represent a hydrogen, methyl, ethyl and halogen atom.
In some embodiments of the invention, X is selected from the following structures:
wherein,
R1-R12the same or different, each independently represent a hydrogen, methyl, ethyl and halogen atom; z represents-S-, -SO2-, -SO-, carbonyl, ester group; r21、R22、R23And R24The same or different, each independently represent a hydrogen, methyl, ethyl and halogen atom.
In some embodiments of the invention, X is selected from the following structures:
wherein,
R1-R6and R11-R12The same or different, each independently represent a hydrogen, methyl, ethyl and halogen atom; z represents-S-, -SO2-, -SO-, carbonyl, ester group; r22Represents hydrogen, methyl, ethyl and halogen atoms.
In some embodiments of the present invention, preferably, the general formula ii is selected from the following structures:
and
wherein,
m and n are the same or different and each independently represents an integer of 0 to 100, wherein m + n represents 0 or a positive integer of 1 to 100.
In some embodiments of the present invention, preferably, the general formula ii is selected from the following structures:
and
wherein,
m and n are the same or different and each independently represents an integer of 0 to 100, wherein m + n represents 0 or a positive integer of 1 to 100.
In some embodiments of the present invention, preferably, the general formula ii is selected from the following structures:
in some embodiments of the present invention, preferably, the general formula ii is selected from the following structures:
and
in the present invention, there is no particular requirement for the individual values of m and n. In the present invention, when the value of m + n is not zero, the molecular weight range is 1000-10000, preferably 1500-7500. The molecular weight range of the present invention refers to the number average molecular weight obtained by a gel chromatography method using a gel chromatograph.
The polyphenylene ether resins of formula II can be prepared as follows:
step 1, dissolving high molecular weight polyphenyl ether into a good solvent, adding an initiator and a corresponding bisphenol monomer, stirring and reacting for a plurality of hours at a certain temperature, and adding a poor solvent to precipitate a solid.
The good solvent can be selected from toluene, butanone and cyclohexanone. Toluene is preferred.
The initiator can be selected from conventional initiators such as AIBN (azobisisobutyronitrile) and BPO (benzoyl peroxide). Preferably BPO.
The temperature range is 40-160 ℃. Preferably 110 deg.C
The reaction time is 0.5-24 hours. Preferably 6 hours.
And 2, dissolving the precipitated solid in a good solvent, adding sodium methoxide, 4-bromobenzocyclobutene and a catalyst, heating and refluxing for several hours, reacting for several hours, and purifying to obtain the modified polyphenyl ether resin shown in the general formula II.
The good solvent can be selected from toluene, butanone and cyclohexanone. Toluene is preferred.
The catalyst is monovalent cupric salt, such as cuprous chloride, cuprous bromide, and cuprous iodide. Cuprous chloride is preferred.
The temperature range is 80-160 ℃. Preferably 110 deg.c.
The reaction time is 2-24 hours. Preferably 10 hours.
The present invention also provides a composition comprising the polyphenylene ether resin compound represented by the general formula I.
The invention also provides a composition containing the polyphenylene ether resin compound shown in the general formula II.
The invention also provides a composition containing the polyphenyl ether resin compound shown in the general formula I and the general formula II.
The invention also provides a modified polyphenyl ether resin containing the general formula I or the general formula II and application of the modified polyphenyl ether resin containing the general formula I or the general formula II and the composition thereof in prepregs.
The invention also provides an application of the prepreg in a copper-clad plate.
The polyphenylene ether resin shown in the general formula I or the general formula II and the composition thereof can be prepared into a prepreg through the following steps:
dissolving modified polyphenyl ether resin shown in general formula I or general formula II and composition thereof in a proper solvent, generally toluene or butanone solution, obtaining 20-60% toluene or butanone solution, adding TAIC (triallyl isocyanurate) with the weight of 10% of the resin, and fully stirring to form glue solution;
immersing reinforcing material, generally glass fiber cloth, paper base, composite material and the like, into the glue solution, keeping for several minutes, taking out the reinforcing material soaked with the glue solution, and removing the solvent to obtain the prepreg.
Compared with the prior art, the modified polyphenylene ether resin with the benzocyclobutene end capping and the epoxy end capping not only keeps the original low dielectric constant and dielectric loss performance of the polyphenylene ether resin, but also has low shrinkage and water absorption, and improves the adhesion to a substrate.
Drawings
FIG. 1 is a carbon spectrum of compound I-1.
FIG. 2 is a carbon spectrum of compound I-5.
Detailed Description
The invention will be illustrated below with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.
Example 1
Preparation of Compound II-a-1
1kg of a high-molecular polyphenylene ether was dissolved in 10L of a toluene solution, and the solution was heated and stirred to be sufficiently dissolved. BPO and bisphenol A were added in an amount of 10% by weight. The reaction was maintained at 110 ℃ for 6 hours.
After the reaction was terminated, most of the toluene solution was removed under reduced pressure, and 5L of methanol was added to precipitate 930g of a white solid, which was designated as resin a.
The resin a was dissolved in toluene, and 10g of sodium methoxide, 10g of 4-bromobenzocyclobutene and 10g of cuprous chloride were added again to react at 110 ℃ for 10 hours. After cooling, the solution is filtered, the solvent is evaporated, and methanol is added to separate out solid, namely the required compound II-a-1.
Example 2
Preparation of Compound II-a-2
1kg of a high-molecular polyphenylene ether was dissolved in 10L of a toluene solution, and the solution was heated and stirred to be sufficiently dissolved. BPO and tetramethyl bisphenol A are added in the amount of 10 percent by weight. The reaction was maintained at 110 ℃ for 6 hours.
After the reaction was stopped, most of the toluene solution was removed under reduced pressure, and 5L of methanol was added to precipitate 960g of a white solid, which was designated as resin b.
The resin b was dissolved in toluene and reacted again with 10g of sodium methoxide, 10g of 4-bromobenzocyclobutene and 10g of cuprous chloride at 110 ℃ for 10 hours. After cooling, the solution is filtered, the solvent is evaporated, and methanol is added to separate out solid, namely the required compound II-a-2.
Example 3
Preparation of Compound II-f-1
1kg of a high-molecular polyphenylene ether was dissolved in 10L of a toluene solution, and the solution was heated and stirred to be sufficiently dissolved. BPO and hexafluorobisphenol A were added in an amount of 10% by weight. The reaction was maintained at 110 ℃ for 6 hours.
After the reaction was stopped, most of the toluene solution was removed under reduced pressure, and 5L of methanol was added to precipitate 910g of a white solid, which was designated as resin c.
The resin c was dissolved in toluene and reacted again with 10g of sodium methoxide, 10g of 4-bromobenzocyclobutene and 10g of cuprous chloride at 110 ℃ for 10 hours. After cooling, the solution is filtered, the solvent is evaporated, and methanol is added to separate out a solid, namely the required compound II-f-1.
Example 4
Preparation of Compound II-e-3
1kg of a high-molecular polyphenylene ether was dissolved in 10L of a toluene solution, and the solution was heated and stirred to be sufficiently dissolved. BPO and bisphenol S were added in an amount of 10% by weight. The reaction was maintained at 110 ℃ for 6 hours.
After the reaction was stopped, most of the toluene solution was removed under reduced pressure, and then 5L of methanol was added to precipitate 850g of a white solid, which was designated as resin d.
The resin d was dissolved in toluene and reacted again with 10g of sodium methoxide, 10g of 4-bromobenzocyclobutene and 10g of cuprous chloride at 110 ℃ for 10 hours. After cooling, the solution is filtered, the solvent is evaporated, and methanol is added to separate out a solid, namely the required compound II-e-3.
Example 5
Preparation of Compound II-b-2
1kg of a high-molecular polyphenylene ether was dissolved in 10L of a toluene solution, and the solution was heated and stirred to be sufficiently dissolved. BPO and tetramethyl biphenyl bisphenol with the weight percentage of 10 percent are added. The reaction was maintained at 110 ℃ for 6 hours.
After the reaction was stopped, most of the toluene solution was removed under reduced pressure, and 5L of methanol was added to precipitate 960g of a white solid, which was designated as resin e.
The resin e was dissolved in toluene and reacted again with 10g of sodium methoxide, 10g of 4-bromobenzocyclobutene and 10g of cuprous chloride at 110 ℃ for 10 hours. After cooling, the solution is filtered, the solvent is evaporated, and methanol is added to separate out solid, namely the required compound II-b-2.
Example 6
Preparation of Compound II-3-2
1kg of a high-molecular polyphenylene ether was dissolved in 10L of a toluene solution, and the solution was heated and stirred to be sufficiently dissolved. BPO and methylbisphenol fluorene are added in an amount of 10% by weight. The reaction was maintained at 110 ℃ for 6 hours.
After the reaction was stopped, most of the toluene solution was removed under reduced pressure, and 5L of methanol was added to precipitate 980g of a white solid, which was designated as resin f.
The resin f was dissolved in toluene and reacted again with 10g of sodium methoxide, 10g of 4-bromobenzocyclobutene and 10g of cuprous chloride at 110 ℃ for 10 hours. After cooling, the solution is filtered, the solvent is evaporated, and methanol is added to separate out solid, namely the required compound II-3-2.
Example 7
Preparation of Compound II-6-1
1kg of a high-molecular polyphenylene ether was dissolved in 10L of a toluene solution, and the solution was heated and stirred to be sufficiently dissolved. BPO and bisphenol X were added in an amount of 10% by weight. The reaction was maintained at 110 ℃ for 6 hours.
After the reaction was stopped, most of the toluene solution was removed under reduced pressure, and 5L of methanol was added to precipitate 960g of a white solid, which was designated as resin g.
The resin g was dissolved in toluene, and 10g of sodium methoxide, 10g of 4-bromobenzocyclobutene and 10g of cuprous chloride were added again to react at 110 ℃ for 10 hours. After cooling, the solution is filtered, the solvent is evaporated, and methanol is added to separate out solid, namely the required compound II-6-1.
Example 8
10g of the compound (12F) was dissolved in toluene, and 10g of sodium methoxide, 10g of 4-bromobenzocyclobutene and 10g of cuprous chloride were added again to react at 110 ℃ for 10 hours. After cooling, the solution is filtered, the solvent is evaporated, and methanol is added to separate out solid, namely the required compound II-10-1-1.
Compound (12F) is shown below:
example 9
Preparation of Compound II-8-1-1
10g of the compound (PhDCPD) are dissolved in toluene and reacted once more with 10g of sodium methoxide, 10g of 4-bromobenzocyclobutene and 10g of cuprous chloride at 110 ℃ for 10 hours. After cooling, the solution is filtered, the solvent is evaporated, and methanol is added to separate out solid, namely the required compound II-8-1-1.
Compound (PhDCPD) is shown below:
example 10
Preparation of Compound I-1
1kg of a high-molecular polyphenylene ether was dissolved in 10L of a toluene solution, and the solution was heated and stirred to be sufficiently dissolved. Adding 10 weight percent of BPO and tetramethyl diphenol. The reaction was maintained at 110 ℃ for 6 hours.
After the reaction was terminated, most of the toluene solution was removed under reduced pressure, and 5L of methanol was added to precipitate 930g of a white solid as resin e 1.
Dissolving the resin e1 in isopropanol, sequentially adding epichlorohydrin and tetrabutylammonium chloride, reacting for 2 hours at 60 ℃, dropwise adding 10% NaOH aqueous solution, and reacting for 2 hours after dropwise adding. And (3) cooling, performing rotary evaporation to remove an organic phase, dissolving the solid with acetone, filtering insoluble substances, and adding methanol into the filtrate to separate out the solid.
The solid thus obtained is the compound corresponding to formula I-1. Carbon spectrum test solvent: deuterated chloroform as shown in figure 1.
Example 11
Preparation of Compound I-3
1kg of a high-molecular polyphenylene ether was dissolved in 10L of a toluene solution, and the solution was heated and stirred to be sufficiently dissolved. BPO and bisphenol OPA were added in an amount of 10% by weight. The reaction was maintained at 110 ℃ for 6 hours.
After the reaction was terminated, most of the toluene solution was removed under reduced pressure, and 5L of methanol was added to precipitate 930g of a white solid as resin e 2.
Bisphenol OPA is represented by the formula:
dissolving the resin e2 in isopropanol, sequentially adding epichlorohydrin and tetrabutylammonium chloride, reacting for 2 hours at 60 ℃, dropwise adding 10% NaOH aqueous solution, and reacting for 2 hours after dropwise adding. And (3) cooling, performing rotary evaporation to remove an organic phase, dissolving the solid with acetone, filtering insoluble substances, and adding methanol into the filtrate to separate out the solid.
The solid obtained is the compound corresponding to formula I-3.
Example 12
Preparation of Compound I-5
1kg of a high-molecular polyphenylene ether was dissolved in 10L of a toluene solution, and the solution was heated and stirred to be sufficiently dissolved. BPO and methylbisphenol fluorene are added in an amount of 10% by weight. The reaction was maintained at 110 ℃ for 6 hours.
After the reaction was terminated, most of the toluene solution was removed under reduced pressure, and 5L of methanol was added to precipitate 930g of a white solid as resin e 3.
Dissolving the resin e3 in isopropanol, sequentially adding epichlorohydrin and tetrabutylammonium chloride, reacting for 2 hours at 60 ℃, dropwise adding 10% NaOH aqueous solution, and reacting for 2 hours after dropwise adding. And (3) cooling, performing rotary evaporation to remove an organic phase, dissolving the solid with acetone, filtering insoluble substances, and adding methanol into the filtrate to separate out the solid.
The solid obtained is the compound corresponding to formula I-5. Carbon spectrum test solvent: deuterated chloroform as shown in figure 2.
Example 13
Preparation of Compound I-9
1kg of a high-molecular polyphenylene ether was dissolved in 10L of a toluene solution, and the solution was heated and stirred to be sufficiently dissolved. BPO and 9, 10-dihydroxyanthracene are added in a weight percentage of 10 percent. The reaction was maintained at 110 ℃ for 6 hours.
After the reaction was terminated, most of the toluene solution was removed under reduced pressure, and 5L of methanol was added to precipitate 930g of a white solid as resin e 4.
Dissolving the resin e4 in isopropanol, sequentially adding epichlorohydrin and tetrabutylammonium chloride, reacting for 2 hours at 60 ℃, dropwise adding 10% NaOH aqueous solution, and reacting for 2 hours after dropwise adding. And (3) cooling, performing rotary evaporation to remove an organic phase, dissolving the solid with acetone, filtering insoluble substances, and adding methanol into the filtrate to separate out the solid.
The solid obtained is the compound corresponding to formula I-9.
According to the prepreg manufacturing method, a corresponding prepreg (hereinafter referred to as PP) was manufactured, and a performance test was performed according to IPC-TM-650.
The polyphenylene ether resin used in the comparative examples is shown in formula SS.
The shrinkage of the epoxy resin was measured by curing 2 parts of epoxy and 1 part of diamine (NN) at 180 ℃ for 2 hours, and measuring the volume before curing and the volume after curing, respectively.
Table 1: performance data of prepregs
PP example 1 PP example 2 PP example 3 Comparative examples
Composition of Ⅰ-1 Ⅰ-5 I-1 and I-5 SS
Ratio of 100％ 100％ 50 percent and 50 percent 100％
Dk 4.21 4.19 4.16 4.43
Df 0.0099 0.0088 0.0085 0.0125
Shrinkage rate 1％ 1.5％ 1.3％ 1.3％
Water absorption rate 0.51 0.55 0.51 0.53
Adhesion force Good taste Good taste Good taste Good taste
Table 2: performance data of prepregs
PP example 5 PP example 6 PP example 7 PP example 8
Composition of Ⅱ-a-2 Ⅱ-b-2 Ⅱ-3-2 I-1 and II-b-2
Ratio of 100％ 100％ 100％ 50 percent and 50 percent
Dk 3.21 3.16 3.06 3.83
Df 0.0049 0.0038 0.0035 0.0065
Shrinkage rate 2％ 2.5％ 2.3％ 1.8％
Water absorption rate 0.61 0.65 0.66 0.58
Adhesion force Good taste Good taste Good taste Good taste
As can be seen from the above examples, the polyphenylene ether resin of the present invention has low shrinkage, low water absorption, good adhesion, and the prepared sheet material has excellent DkDf performance.

Claims (10)

1. A polyphenylene ether resin having the structure of formula I:
wherein,
said Z represents an aromatic diphenol structure selected from the group consisting of:
the R is31And R32The same or different, each independently represents hydrogen or methyl;
me represents a methyl group, Et represents an ethyl group;
p, q, r, s, t, u and v are the same or different and each independently represents 0, 1 or 2;
and a and b are the same or different and each independently represent an integer of 0 to 100, wherein m + n represents a positive integer of 1 to 100.
2. The polyphenylene ether resin of claim 1, wherein the general formula i is selected from the following structures:
3. the polyphenylene ether resin of claim 1, wherein the general formula i is selected from the following structures:
and
4. a polyphenylene ether resin having the structure of formula ii:
wherein,
the X is an aromatic diphenol structure selected from the group consisting of:
wherein,
the R is1-R12The same or different, each independently represent a hydrogen, methyl, ethyl and halogen atom;
z represents-S-, -SO2-, -SO-, carbonyl, ester group;
the R is21、R22、R23And R24The same or different, each independently represent a hydrogen, methyl, ethyl and halogen atom;
the m and the n are the same or different and respectively and independently represent an integer of 0-100, wherein m + n represents 0 or a positive integer of 1-100.
5. The polyphenylene ether resin of claim 4, wherein the formula II is selected from the following structures:
and
and
wherein,
m and n are the same or different and each independently represents an integer of 0 to 100, wherein m + n represents 0 or a positive integer of 1 to 100.
6. The polyphenylene ether resin of claim 4, wherein the formula II is selected from the following structures:
and
7. a composition comprising at least one of the polyphenylene ether resins of claims 1-6.
8. The composition of claim 7, wherein the composition comprises at least one polyphenylene ether resin according to formula I and at least one polyphenylene ether resin according to formula II.
9. A prepreg prepared from the polyphenylene ether resin according to any one of claims 1 to 6 or the composition according to any one of claims 7 to 8.
10. The use of the semi-cured adhesive sheet of claim 9 in the preparation of copper clad laminate.
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CN112898561A (en) * 2021-01-27 2021-06-04 大连理工大学 Maleimide-terminated polyphenylene ether and preparation method thereof
CN114573426A (en) * 2022-04-02 2022-06-03 江门建滔电子发展有限公司 Benzocyclobutene derivative and application thereof

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