CN104263306B

CN104263306B - The preparation method of a kind of polyphenylene oxide sizing agent and copper-clad plate thereof

Info

Publication number: CN104263306B
Application number: CN201410506080.8A
Authority: CN
Inventors: 代三威; 黄杰; 吴学明
Original assignee: Sichuan Dongcai Technology Group Co Ltd
Current assignee: Sichuan Dongcai Technology Group Co Ltd
Priority date: 2014-09-26
Filing date: 2014-09-26
Publication date: 2016-02-10
Anticipated expiration: 2034-09-26
Also published as: CN104263306A

Abstract

The invention discloses a kind of polyphenylene oxide sizing agent, it is characterized in that: mixed by the component raw material of resin combination 100 mass parts, fire retardant 0 ~ 15 mass parts, powder body material 20 ~ 30 mass parts, curing catalyst 0.1 ~ 2 mass parts and solvent 50 ~ 100 mass parts and quality proportioning and form; Described resin combination is mixed by the component raw material of modified low molecular weight polyphenylene oxide resin 20 ~ 65 mass parts, epoxy resin 15 ~ 40 mass parts, benzoxazine colophony 20 ~ 40 mass parts, bimaleimide resin 3 ~ 9 mass parts and quality proportioning and forms.Through preparing modified low molecular weight polyphenylene oxide resin, prepare resin combination, the step such as preparation polyphenylene oxide sizing agent obtains.Adopt polyphenylene oxide sizing agent of the present invention to prepare polyphenylene oxide glasscloth prepreg through adhesive applicator coating, then prepare copper-clad plate through vacuum press; Obtained copper-clad plate has good dielectric properties.

Description

The preparation method of a kind of polyphenylene oxide sizing agent and copper-clad plate thereof

Technical field

The invention belongs to tackiness agent and Synthesis and applications thereof, relate to a kind of polyphenylene oxide sizing agent and preparation method thereof and the preparation method for copper-clad plate.Polyphenylene oxide sizing agent of the present invention, is suitable for the sizing agent doing prepreg and copper-clad plate in electronic and electrical equipment, and the copper-clad plate using sizing agent of the present invention to prepare has good dielectric properties.

Background technology

Along with the develop rapidly of information industry, the baseplate material of printed circuit board is had higher requirement, require that it has lower specific inductivity and dielectric loss, high glass-transition temperature, high heat resistance, low water absorption.Traditional epoxy laminated board cannot meet the requirement of electronics printed circuit board, needs to find the better matrix resin of performance.

Polyphenylene oxide resin (being called for short PPE) has higher mechanical strength and thermotolerance, good stability of the dimension, rate of moisture absorption is low, specific inductivity and dielectric loss are hardly by temperature, the over-all properties that the impact of humidity and frequency etc. are good, can be applicable to the dielectric properties of electric field, particularly high glass-transition temperature and excellence, is one of desirable equivalent material of high performance copper clad laminate base material.But because existing polyphenylene oxide resin melt temperature is too high, melting viscosity is high, and fluidity of molten is too poor, is unfavorable for the preparation of printed circuit board, thus limit its application on high-performance printed circuit board.

Summary of the invention

Object of the present invention is intended to overcome above-mentioned deficiency of the prior art, provides a kind of polyphenylene oxide sizing agent and preparation method thereof, thus provides the polyphenylene oxide sizing agent of a kind of prepreg for making printed circuit board of good performance and copper-clad plate.

Another object of the present invention is to provide the application method of a kind of polyphenylene oxide sizing agent at printed circuit board prepreg, copper-clad base plate, and obtained copper clad laminate has outstanding dielectric properties, can use as high frequency printed circuit board.

A content of the present invention is: a kind of polyphenylene oxide sizing agent, is characterized in that: this polyphenylene oxide sizing agent is mixed by the component raw material of resin combination 100 mass parts, fire retardant 0 ~ 15 mass parts, powder body material 20 ~ 30 mass parts, curing catalyst 0.1 ~ 2 mass parts and solvent 50 ~ 100 mass parts and quality proportioning and forms; And at room temperature, be the glue between 200 ~ 320 seconds by above-mentioned material circular hole method molding time under joining glue tank to be made into 171 DEG C of hot plates, i.e. polyphenylene oxide sizing agent;

Described resin combination is mixed by the component raw material of modified low molecular weight polyphenylene oxide resin 20 ~ 65 mass parts, epoxy resin 15 ~ 40 mass parts, benzoxazine colophony 20 ~ 40 mass parts, bimaleimide resin 3 ~ 9 mass parts and quality proportioning and forms;

Described epoxy resin can be bisphenol A type epoxy resin, brominated epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol aldehyde type epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, and containing one or more the mixture in the structural epoxy resins such as dipentadiene, aliphatics, phenyl ring, naphthalene nucleus, biphenyl;

The structure of described epoxy resin and molecular weight do not have the requirement of specific, concrete, and described epoxy resin preferred structure symmetry and epoxy equivalent (weight) are not more than the epoxy resin of 700, contribute to the compatible of each component like this, also contribute to the dipping of glasscloth;

Described benzoxazine colophony can be any one in phenol type benzoxazine colophony, bisphenol A-type benzoxazine colophony, bisphenol-f type benzoxazine colophony, bisphenol S type benzoxazine colophony, phenolic benzoxazine resin and two amine type benzoxazine colophonies;

Described fire retardant can be decabromodiphynly oxide, TDE, melamine polyphosphate, three (2,6-xylyl) phosphorus, 9,10-dihydro-9-oxy is mixed one or more the mixture in-10-phospho hetero phenanthrene-10-oxide compound (be called for short DOPO), 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (being called for short DOPO-DN), hexachlorocyclotriphosphazene, alkoxycyclotriphosphderivative, phenoxy group three phosphonitrile, phosphorus containing phenolic resin; Although modified low molecular weight polyphenylene oxide resin itself has certain flame retardant resistance, for fire-retardant there is high request time, also need to add certain above-mentioned fire retardant, the fire retardant of interpolation can be addition type, also can be response type.

Described powder body material can be one or more the composition in aluminium hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, silicon powder, talcum powder, zinc borate, mica, boron nitride;

Described curing catalyst can be one or more the composition in boron trifluoride ethylamine, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, triphenylphosphine, tributylphosphine, triethyl phosphine;

Described solvent can be one or more the mixture in toluene, dimethylbenzene, acetone, butanone;

The preparation method of described modified low molecular weight polyphenylene oxide resin is: first, add 100 mass parts polyphenylene oxide, 200 ~ 300 mass parts toluene in the reactor, be warming up to 80 ~ 90 DEG C and stir polyphenylene oxide particles is dissolved, add 12 ~ 20 mass parts diallyl bisphenols or tetraallyl dihydroxyphenyl propane again, be under the condition of 30 ~ 90 DEG C in temperature of reaction, drip with 0.5h or gradation add the peroxide initiator of 2.5 ~ 4 mass parts after, react stopped reaction after 1 ~ 10h again; Second, in reactor, add the alkali metal hydroxide of 1.4 ~ 2.2 mass parts and the phase-transfer catalyst of 1 ~ 2 mass parts, at the temperature of 40 ~ 70 DEG C, drip the chlorallylene of 18 ~ 30 mass parts, 0.5 ~ 1h drips off, and continues to react 8 ~ 10h at this temperature; 3rd, by the cut at (polyphenylene oxide resin of the allylation obtained) reaction soln Distillation recovery 60 DEG C, reclaim excessive chlorallylene, adding 18 ~ 30 mass parts mass percentage is the peroxide acetate aqueous solution of 40%, at 30 ~ 60 DEG C of temperature, carry out the reaction times is after 6 ~ 15h, stopped reaction, obtains modified polyphenylene ether resin reaction soln; Finally, the modified polyphenylene ether resin reaction soln deionized water obtained is extracted 3 times, each water consumption is 1/3rd of solvent toluene quality, extract rear combining extraction liquid, redistillation gone out most solvent toluene, again surplus solution is added drop-wise in 300 mass parts Methanol, namely modified polyphenylene ether resin can separate out, precipitation, filtration, and solids is again with after 50 mass parts Methanol/time washing 3 times, drying, i.e. obtained (grey powder) modified low molecular weight polyphenylene oxide resin;

In the preparation method of described modified low molecular weight polyphenylene oxide resin:

Described polyphenylene oxide is poly-2,6-dimethyl-Isosorbide-5-Nitrae-phenylate, can be the product of commercially available any company;

Described diallyl bisphenol, tetraallyl dihydroxyphenyl propane are respectively the compound of following structural:

Described initiator can be one or more the composition in benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, peroxidation trimethylacetic acid tertiary butyl ester, methylethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate;

Described alkali metal hydroxide can be one or more the mixture in lithium hydroxide, sodium hydroxide, potassium hydroxide;

Described phase-transfer catalyst is quaternary ammonium compound, can be one or more the composition in benzyltriethylammoinium chloride (being called for short TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate (being called for short TBAB), tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride;

The preparation method of described polyphenylene oxide sizing agent, is characterized in that there is the following step:

A, prepare modified low molecular weight polyphenylene oxide resin, its preparation method is: first, add 100 mass parts polyphenylene oxide, 200 ~ 300 mass parts toluene in the reactor, be warming up to 80 ~ 90 DEG C and stir polyphenylene oxide particles is dissolved, add 12 ~ 20 mass parts diallyl bisphenols or tetraallyl dihydroxyphenyl propane again, be under the condition of 30 ~ 90 DEG C in temperature of reaction, drip with 0.5h or gradation add the peroxide initiator of 2.5 ~ 4 mass parts after, react stopped reaction after 1 ~ 10h again; Second, in reactor, add the alkali metal hydroxide of 1.4 ~ 2.2 mass parts and the phase-transfer catalyst of 1 ~ 2 mass parts, at the temperature of 40 ~ 70 DEG C, drip the chlorallylene of 18 ~ 30 mass parts, 0.5 ~ 1h drips off, and continues to react 8 ~ 10h at this temperature; 3rd, by the cut at (polyphenylene oxide resin of the allylation obtained) reaction soln Distillation recovery 60 DEG C, reclaim excessive chlorallylene, adding 18 ~ 30 mass parts mass percentage is the peroxide acetate aqueous solution of 40%, at 30 ~ 60 DEG C of temperature, carry out the reaction times is after 6 ~ 15h, stopped reaction, obtains modified polyphenylene ether resin reaction soln; Finally, the modified polyphenylene ether resin reaction soln deionized water obtained is extracted 3 times, each water consumption is 1/3rd of solvent toluene quality, extract rear combining extraction liquid, redistillation gone out most solvent toluene, again surplus solution is added drop-wise in 300 mass parts Methanol, namely modified polyphenylene ether resin can separate out, precipitation, filtration, and solids is again with after 50 mass parts Methanol/time washing 3 times, drying, i.e. obtained (grey powder) modified low molecular weight polyphenylene oxide resin;

B, prepare resin combination: get each component raw material, mixing composition resin combination by the component raw material of modified low molecular weight polyphenylene oxide resin 20 ~ 65 mass parts, epoxy resin 15 ~ 40 mass parts, benzoxazine colophony 20 ~ 40 mass parts, bimaleimide resin 3 ~ 12 mass parts and quality proportioning;

Described epoxy resin can be bisphenol A type epoxy resin, brominated epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol aldehyde type epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset or containing one or more the mixture in the structural epoxy resins such as dipentadiene, aliphatics, phenyl ring, naphthalene nucleus, biphenyl;

C, preparation polyphenylene oxide sizing agent:

Each component raw material is got by the component raw material of resin combination 100 mass parts, fire retardant 0 ~ 15 mass parts, powder body material 20 ~ 30 mass parts, curing catalyst 0.1 ~ 2 mass parts and solvent 50 ~ 100 mass parts and quality proportioning;

At room temperature, the resin combination of formula ratio, fire retardant, powder body material and solvent being joined joins in glue tank, stir 1 ~ 2h at the temperature of room temperature to 50 DEG C after, add the curing catalyst of formula ratio again, after continuing stirring 1 ~ 2h (to being uniformly dissolved), sampling detects, when under 171 DEG C of hot plates, circular hole method molding time is between 200 ~ 320 seconds, namely the preparation of polyphenylene oxide sizing agent is completed, obtained polyphenylene oxide sizing agent;

Described fire retardant can be decabromodiphynly oxide, TDE, melamine polyphosphate, three (2,6-xylyl) phosphorus, 9,10-dihydro-9-oxy is mixed one or more the mixture in-10-phospho hetero phenanthrene-10-oxide compound (be called for short DOPO), 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (being called for short DOPO-DN), hexachlorocyclotriphosphazene, alkoxycyclotriphosphderivative, phenoxy group three phosphonitrile, phosphorus containing phenolic resin;

Described solvent can be one or more the mixture in toluene, dimethylbenzene, acetone, butanone.

Another content of the present invention is: a kind of polyphenylene oxide sizing agent is used for the preparation method of copper-clad plate, it is characterized in that there is the following step:

The preparation method of polyphenylene oxide sizing agent described in a, use the present invention one content, the polyphenylene oxide sizing agent described in preparation the present invention one content, for subsequent use;

B, prepare polyphenylene oxide glasscloth prepreg:

Polyphenylene oxide sizing agent described in glasscloth 2116 is applied by adhesive applicator, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 70 DEG C ~ 165 DEG C, the speed of a motor vehicle (or claiming linear speed) of adhesive applicator is 2 ~ 10m/min, to the glasscloth 2116 of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, namely obtained polyphenylene oxide glasscloth prepreg, for subsequent use;

C, prepare copper-clad plate by prepreg:

Polyphenylene oxide glasscloth prepreg is cut into product desired size, by product desired thickness by one deck or two-layer above polyphenylene oxide glasscloth prepreg overlap, single or double mixes alligatoring Copper Foil, be placed on smooth stainless steel plate, be placed in vacuum press, (with substantially not gummosis be as the criterion) increasing temperature and pressure gradually, finally when hot plate temperature be 180 ~ 220 DEG C, pressure is 78 ~ 90 ㎏/cm ^2,time, determine to continue hot pressing time between 1 ~ 2h according to the thickness of sheet material, i.e. obtained polyphenylene oxide copper-clad plate.

Compared with prior art, the present invention has features and beneficial effect:

(1) in the present invention, modified low molecular weight polyphenylene oxide resin solvability in toluene is good, and the good fluidity of at high temperature resin, there is the excellent compatibility with the material such as benzoxazine resin, epoxy resin, its composition glue of easily extensible increases other composition or reduces existing composition and consumption thereof, improves the possibility improving its difference in functionality and purposes;

(2) the present invention adopts the bis-phenol of band double bond to polyphenylene oxide resin of reallocating, introduce more double bond, after further epoxidation, make can have more epoxide group in the modified low molecular weight polyphenylene oxide resin obtained, more epoxide group has larger cross-linking density after can ensureing resin solidification, more outstanding thermotolerance;

(3) in the present invention, the end moieties of modified low molecular weight polyphenylene oxide resin, except major part is epoxide group, also contains the hydroxyl do not reacted in few partially modified process and double bond;

(4) the present invention is adopted, because modified low molecular weight polyphenylene oxide resin and epoxy resin, benzoxazine colophony, bimaleimide resin combinationally use; The polyphenylene oxide sizing agent that molecular weight because of modified low molecular weight polyphenylene oxide resin is little and make it prepare there is the less feature of dependent viscosity, be greatly conducive to dipping produce its cloth prepreg;

(5) the present invention is adopted, multiple reaction can be there is when solidifying in polyphenylene oxide sizing agent, exist epoxy group(ing), can ring-opening polymerization be there is between hydroxyl and benzoxazinyl group, also the crosslinked further of Diene-addition and adduct can be there is between double bond and bismaleimides, and because of these differing tempss of reacting, extremely be conducive to its glasscloth veneer sheet point temperature section in thermoforming process to be cross-linked, improve cross-linking density, reduce the control difficulty of its veneer sheet heat curing process, improve the yield rate of veneer sheet;

(6) product preparation process route of the present invention is simple, and reaction yield is high, and the three wastes are less, easily operates, and raw materials used all have industrialization product, is conducive to large-scale popularization and industrialization, practical.

Embodiment

The invention will be further described for embodiment plan given below; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.

The preparation of modified low molecular weight polyphenylene oxide resin:

Modified low molecular weight polyphenylene oxide resin I

First, is furnished with reflux condensing tube unsealed, in the reactor A of stirring, thermopair, add 100 ㎏ polyphenylene oxide (Asahi Chemical Corp, commodity are called S201A, and number-average molecular weight is 20000), add 240 ㎏ toluene and make solvent, being warmed up to 90 DEG C and stirring makes polyphenylene oxide particles dissolve completely, add 15.5 ㎏ diallyl bisphenols again, at 55 DEG C, add the benzoyl peroxide of 3.2 ㎏, 0.5h divides and adds for 6 times, stopped reaction after reaction 3h.The second, in reactor A, add 2.2 ㎏ sodium hydroxide and 1 ㎏ Tetrabutyl amonium bromide, at the temperature of 50 DEG C, drip 30 ㎏ chlorallylenes, 1h drips off, and continues to react 8h at this temperature, obtains the polyphenylene oxide resin reaction soln of allylation.3rd, the polyphenylene oxide resin reaction soln of the allylation obtained in reactor A is distilled, the cut at reclaiming 60 DEG C.Without adding 18 ㎏ Peracetic Acid (content is 40%) after overhead product, 60 DEG C of reaction 6h, the modified low molecular weight polyphenylene oxide resin reaction soln obtained.

Finally, the modified low molecular weight polyphenylene oxide resin reaction soln deionized water obtained in reactor A is extracted three times, each water consumption is 80 ㎏, about 180 ㎏ toluene are steamed after having extracted, again surplus solution is added drop-wise in 300 ㎏ methyl alcohol, by the sedimentation and filtration of separating out, with 50 ㎏ methyl alcohol/time washing three times, after drying, obtain 103.1 ㎏ grey powder products.

Modified low molecular weight polyphenylene oxide resin II

First, be furnished with reflux condensing tube unsealed, in the reactor A of stirring, thermopair, add 100 ㎏ polyphenylene oxide (blue star green woods, commodity are called LXR35, number-average molecular weight is 22000--28000), add 300 ㎏ toluene and make solvent, be warmed up to 85 DEG C and stir polyphenylene oxide particles is dissolved completely, add 20 ㎏ tetraallyl dihydroxyphenyl propanes again, at 90 DEG C, the disposable benzoyl peroxide adding 4 ㎏, stopped reaction after reaction 4h.The second, in reactor A, add 1.8 ㎏ sodium hydroxide and 2 ㎏ Tetrabutyl amonium bromides, at the temperature of 40 DEG C, drip 20 ㎏ chlorallylenes, 0.75h drips off, and continues to react 6h at this temperature, obtains the polyphenylene oxide resin reaction soln of allylation.3rd, the polyphenylene oxide resin reaction soln of the allylation obtained in reactor A is distilled, the cut at reclaiming 60 DEG C.To without adding 24 ㎏ Peracetic Acid (content is 40%) after overhead product, 45 DEG C of reaction 12h, the modified low molecular weight polyphenylene oxide resin reaction soln obtained.

Finally, the modified polyphenylene ether resin reaction soln deionized water obtained in reactor A is extracted three times, each water consumption is 100 ㎏, about 240 ㎏ toluene are steamed after having extracted, again surplus solution is added drop-wise in 300 ㎏ methyl alcohol, by the sedimentation and filtration of separating out, with 50 ㎏ methyl alcohol/time washing three times, after drying, obtain 110.9 ㎏ grey powder products.

Modified low molecular weight polyphenylene oxide resin III

First, is furnished with reflux condensing tube unsealed, in the reactor A of stirring, thermopair, add 100 ㎏ polyphenylene oxide (blue star green woods, commodity are called LXR40, and number-average molecular weight is 30000--37000), add 180 ㎏ toluene and make solvent, being warmed up to 80 DEG C and stirring makes polyphenylene oxide particles dissolve completely, add 12 ㎏ diallyl bisphenols again, at 30 DEG C, add the di-t-butyl peroxide of 2.5 ㎏, 0.5h divides and adds for 4 times, stopped reaction after reaction 5h.The second, in reactor A, add 1.4 ㎏ sodium hydroxide and 1.15 ㎏ tetrabutylammonium chlorides, at the temperature of 70 DEG C, drip 18 ㎏ chlorallylenes, 0.5h drips off, and continues to react 10h at this temperature, obtains the polyphenylene oxide resin reaction soln of allylation.3rd, the polyphenylene oxide resin reaction soln of the allylation obtained in reactor A is distilled, the cut at reclaiming 60 DEG C.To without adding 30 ㎏ Peracetic Acid (content is 40%) after overhead product, 30 DEG C of reaction 15h, the modified low molecular weight polyphenylene oxide resin reaction soln obtained.

Finally, the modified low molecular weight polyphenylene oxide resin reaction soln deionized water obtained in reactor A is extracted three times, each water consumption is 60 ㎏, about 120 ㎏ toluene are steamed after having extracted, again surplus solution is added drop-wise in 300 ㎏ methyl alcohol, by the sedimentation and filtration of separating out, with 50 ㎏ methyl alcohol/time washing three times, after drying, obtain 102.3 ㎏ grey powder products.

Embodiment 1:

At room temperature get resin combination 100 ㎏ (above-mentioned modified low molecular weight polyphenylene oxide resin I 50 ㎏, Tao Shi 383 epoxy resin 29.4 ㎏, bisphenol A benzoxazine resin 16 ㎏, bimaleimide resin 4.6 ㎏), magnesium hydroxide 25 ㎏, toluene 70 ㎏ and butanone 23 ㎏ add and join in glue tank, stir 1h, add imidazoles 1.3 ㎏, stirring at room temperature 1h, under 171 DEG C of hot plates, circular hole method molding time is 272 seconds, namely completes the preparation of polyphenylene oxide sizing agent.

By glasscloth 2116 by adhesive applicator coating polyphenylene oxide sizing agent, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 70 DEG C ~ 165 DEG C, the speed of a motor vehicle (linear speed) of adhesive applicator is 2 ~ 10m/min, to the glasscloth of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, i.e. obtained prepreg.By superimposed for prepreg cut-parts, two-sidedly mix alligatoring Copper Foil, put on smooth stainless steel plate, be placed in vacuum press, with substantially not gummosis to be as the criterion increasing temperature and pressure gradually, finally when hot plate temperature pressure is 200 DEG C, 78 ㎏/cm ^2,time, after continuing 90min hot-press solidifying, i.e. obtained polyphenylene oxide copper-clad plate.

Embodiment 2:

At room temperature get resin combination 100 ㎏ (above-mentioned modified low molecular weight polyphenylene oxide resin II 50 ㎏, Tao Shi 383 epoxy resin 26.8 ㎏, bisphenol A benzoxazine resin 18 ㎏, bimaleimide resin 5.2 ㎏), talcum powder 26 ㎏, toluene 70 ㎏ and butanone 23 ㎏ add and join in glue tank, stir 2h, add triphenylphosphine 1.3 ㎏, stirred at ambient temperature 1h, under 171 DEG C of hot plates, circular hole method molding time is 291 seconds, namely completes the preparation of polyphenylene oxide sizing agent.

By glasscloth 2116 by adhesive applicator coating polyphenylene oxide sizing agent, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 70 DEG C ~ 165 DEG C, the speed of a motor vehicle (linear speed) of adhesive applicator is 2 ~ 10m/min, to the glasscloth of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, i.e. obtained prepreg.By superimposed for prepreg cut-parts, two-sidedly mix alligatoring Copper Foil, put on smooth stainless steel plate, be placed in vacuum press, with substantially not gummosis to be as the criterion increasing temperature and pressure gradually, finally when hot plate temperature pressure is 200 DEG C, 80 ㎏/cm ^2,time, after continuing 120min hot-press solidifying, i.e. obtained polyphenylene oxide copper-clad plate.

Embodiment 3:

At room temperature get resin combination 100 ㎏ (above-mentioned modified low molecular weight polyphenylene oxide resin III 51 ㎏, Tao Shi 438 epoxy resin 22 ㎏, bisphenol A benzoxazine resin 22.4 ㎏, bimaleimide resin 4.6 ㎏), barium sulfate 28 ㎏, toluene 70 ㎏ and butanone 23 ㎏ add and join in glue tank, 50 DEG C are stirred 1h, add imidazoles 1.6 ㎏, 50 DEG C are stirred 2h, under 171 DEG C of hot plates, circular hole method molding time is 200 seconds, namely completes the preparation of polyphenylene oxide sizing agent.

By glasscloth 2116 by adhesive applicator coating polyphenylene oxide sizing agent, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 70 DEG C ~ 165 DEG C, the speed of a motor vehicle (linear speed) of adhesive applicator is 2 ~ 10m/min, to the glasscloth of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, i.e. obtained prepreg.By superimposed for prepreg cut-parts, two-sidedly mix alligatoring Copper Foil, put on smooth stainless steel plate, be placed in vacuum press, with substantially not gummosis to be as the criterion increasing temperature and pressure gradually, finally when hot plate temperature pressure is 190 DEG C, 85 ㎏/cm ^2,time, after continuing 110min hot-press solidifying, i.e. obtained polyphenylene oxide copper-clad plate.

Embodiment 4:

At room temperature get resin combination 100 ㎏ (above-mentioned modified low molecular weight polyphenylene oxide resin I 49.7 ㎏, Tao Shi 438 epoxy resin 24.8 ㎏, bisphenol A benzoxazine resin 20.9 ㎏, bimaleimide resin 4.6 ㎏), talcum powder 26 ㎏, toluene 70 ㎏ and butanone 23 ㎏ add and join in glue tank, stirring at room temperature 2h, add boron trifluoride ethylamine 1.3 ㎏, stirring at room temperature 1h, under 171 DEG C of hot plates, circular hole method molding time is 283 seconds, namely completes the preparation of polyphenylene oxide sizing agent.

By glasscloth 2116 by adhesive applicator coating polyphenylene oxide sizing agent, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 70 DEG C ~ 165 DEG C, the speed of a motor vehicle (linear speed) of adhesive applicator is 2 ~ 10m/min, to the glasscloth of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, i.e. obtained prepreg.By superimposed for prepreg cut-parts, two-sidedly mix alligatoring Copper Foil, put on smooth stainless steel plate, be placed in vacuum press, with substantially not gummosis to be as the criterion increasing temperature and pressure gradually, finally when hot plate temperature pressure is 210 DEG C, 80 ㎏/cm ^2,time, after continuing 90min hot-press solidifying, i.e. obtained polyphenylene oxide copper-clad plate.

Embodiment 5:

At room temperature get resin combination 100 ㎏ (above-mentioned modified low molecular weight polyphenylene oxide resin III 46.5 ㎏, Tao Shi phosphorous epoxy resin 29.2 ㎏, Bisphenol F benzoxazine resin 16.7 ㎏, bimaleimide resin 6.4 ㎏), calcium carbonate 20 ㎏, toluene 68 ㎏ and butanone 32 ㎏ add and join in glue tank, 40 DEG C are stirred 2h, add imidazoles 1.3 ㎏, 40 DEG C are stirred 1h, under 171 DEG C of hot plates, circular hole method molding time is 293 seconds, namely completes the preparation of polyphenylene oxide sizing agent.

By glasscloth 2116 by adhesive applicator coating polyphenylene oxide sizing agent, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 70 DEG C ~ 165 DEG C, the speed of a motor vehicle (linear speed) of adhesive applicator is 2 ~ 10m/min, to the glasscloth of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, i.e. obtained prepreg.By superimposed for prepreg cut-parts, two-sidedly mix alligatoring Copper Foil, put on smooth stainless steel plate, be placed in vacuum press, with substantially not gummosis to be as the criterion increasing temperature and pressure gradually, finally when hot plate temperature pressure is 185 DEG C, 86 ㎏/cm ^2,time, after continuing 120min hot-press solidifying, i.e. obtained polyphenylene oxide copper-clad plate.

Embodiment 6:

At room temperature get resin combination 100 ㎏ (above-mentioned modified low molecular weight polyphenylene oxide resin I 49.2 ㎏, Tao Shi 383 epoxy resin 30.1 ㎏, bisphenol A benzoxazine resin 15.7 ㎏), bimaleimide resin 4.4 ㎏), phosphorus containing phenolic resin (Huizhou flourishing age reaches) 15 ㎏, silicon powder 23 ㎏, toluene 76 ㎏ and butanone 23 ㎏ join and join in glue tank, stirring at room temperature 1h, add imidazoles 1.5 ㎏, stirring at room temperature 1.5h, under 171 DEG C of hot plates, circular hole method molding time is 277 seconds, namely completes the preparation of polyphenylene oxide sizing agent.

By glasscloth 2116 by adhesive applicator coating polyphenylene oxide sizing agent, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 70 DEG C ~ 165 DEG C, the speed of a motor vehicle (linear speed) of adhesive applicator is 2 ~ 10m/min, to the glasscloth of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, i.e. obtained prepreg.By superimposed for prepreg cut-parts, two-sidedly mix alligatoring Copper Foil, put on smooth stainless steel plate, be placed in vacuum press, with substantially not gummosis to be as the criterion increasing temperature and pressure gradually, finally when hot plate temperature pressure is 180 DEG C, 90 ㎏/cm ^2,time, after continuing 120min hot-press solidifying, i.e. obtained polyphenylene oxide copper-clad plate.

Embodiment 7:

At room temperature get resin combination 100 ㎏ (above-mentioned modified low molecular weight polyphenylene oxide resin II 48.6 ㎏, Tao Shi 438 epoxy resin 29.6 ㎏, phenol type benzoxazine resin 16.6 ㎏, bimaleimide resin 4.6 ㎏), DOPO-HQ (Huizhou flourishing age reaches) 10 ㎏, magnesium hydroxide 30 ㎏, toluene 80 ㎏ and butanone 23 toluene 80 ㎏ and butanone 23 ㎏ join and join in glue tank, stirring at room temperature 1.5h, add imidazoles 2 ㎏, stirring at room temperature 2h, under 171 DEG C of hot plates, circular hole method molding time is 302 seconds, namely completes the preparation of polyphenylene oxide sizing agent.

By glasscloth 2116 by adhesive applicator coating polyphenylene oxide sizing agent, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 70 DEG C ~ 165 DEG C, the speed of a motor vehicle (linear speed) of adhesive applicator is 2 ~ 10m/min, to the glasscloth of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, i.e. obtained prepreg.By superimposed for prepreg cut-parts, two-sidedly mix alligatoring Copper Foil, put on smooth stainless steel plate, be placed in vacuum press, with substantially not gummosis to be as the criterion increasing temperature and pressure gradually, finally when hot plate temperature pressure is 195 DEG C, 82 ㎏/cm ^2,time, after continuing 120min hot-press solidifying, i.e. obtained polyphenylene oxide copper-clad plate.

Embodiment 8:

At room temperature get resin combination 100 ㎏ (above-mentioned modified low molecular weight polyphenylene oxide resin III 50 ㎏, Tao Shi 383 epoxy resin 30.5 ㎏, bisphenol S benzoxazine resin 21 ㎏, bimaleimide resin 4 ㎏), phenoxy group three phosphonitrile 12 ㎏, aluminium hydroxide 20 ㎏, toluene 84 ㎏ and butanone 32 toluene 84 ㎏ and butanone 32 ㎏ join and join in glue tank, 30 DEG C are stirred 2h, add 2-ethyl-4-methylimidazole 1 ㎏, 30 DEG C are stirred 1.5h, under 171 DEG C of hot plates, circular hole method molding time is 320 seconds, namely completes the preparation of polyphenylene oxide sizing agent.

By glasscloth 2116 by adhesive applicator coating polyphenylene oxide sizing agent, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 70 DEG C ~ 165 DEG C, the speed of a motor vehicle (linear speed) of adhesive applicator is 2 ~ 10m/min, to the glasscloth of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, i.e. obtained prepreg.By superimposed for prepreg cut-parts, two-sidedly mix alligatoring Copper Foil, put on smooth stainless steel plate, be placed in vacuum press, with substantially not gummosis to be as the criterion increasing temperature and pressure gradually, finally when hot plate temperature pressure is 220 DEG C, 88 ㎏/cm ^2,time, after continuing 90min hot-press solidifying, i.e. obtained polyphenylene oxide copper-clad plate.

Comparative example 1:

At room temperature, get Tao Shi 383 epoxy resin 50 ㎏, bisphenol A benzoxazine resin 6 ㎏, phosphorus containing phenolic resin (Huizhou flourishing age reaches) 25 ㎏, silicon powder 26 ㎏, toluene 76 ㎏ and butanone 23 ㎏ join and join in glue tank, add imidazoles 1.5 ㎏, after stirring at room temperature 2h, under 171 DEG C of hot plates, circular hole method molding time is 269 seconds, namely completes the preparation of polyphenylene oxide sizing agent.

By glasscloth 2116 by adhesive applicator coating polyphenylene oxide sizing agent, the drying tunnel length of described adhesive applicator is 24m, be divided into 3 sections, every section of 8m, the scope of stoving temperature point gradient is 70 DEG C ~ 165 DEG C, the speed of a motor vehicle (linear speed) of adhesive applicator is 2 ~ 10m/min, to the glasscloth of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, namely obtained prepreg is by superimposed for prepreg cut-parts, two-sidedly mix alligatoring Copper Foil, put on smooth stainless steel plate, be placed in vacuum press, with substantially not gummosis to be as the criterion increasing temperature and pressure gradually, finally when hot plate temperature pressure is 200 DEG C, 80 ㎏/cm ^2,time, after continuing 110min hot-press solidifying, i.e. obtained polyphenylene oxide copper-clad plate.

Comparative example 2:

At room temperature, get Tao Shi phosphorous epoxy resin 50 ㎏, bisphenol A benzoxazine resin 16 ㎏, phosphorus containing phenolic resin (Huizhou flourishing age reaches) 5 ㎏, silicon powder 26 ㎏, toluene 76 ㎏ and butanone 23 ㎏ join and join in glue tank, add 2-ethyl-4-methylimidazole 1.5 ㎏, after stirring at room temperature 2h, under 171 DEG C of hot plates, circular hole method molding time is 275 seconds, namely completes the preparation of polyphenylene oxide sizing agent.

By glasscloth 2116 by adhesive applicator coating polyphenylene oxide sizing agent, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 70 DEG C ~ 165 DEG C, the speed of a motor vehicle (linear speed) of adhesive applicator is 2 ~ 10m/min, to the glasscloth of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, i.e. obtained prepreg.By superimposed for prepreg cut-parts, two-sidedly mix alligatoring Copper Foil, put on smooth stainless steel plate, be placed in vacuum press, with substantially not gummosis to be as the criterion increasing temperature and pressure gradually, finally when hot plate temperature pressure is 190 DEG C, 84 ㎏/cm ^2,time, after continuing 90min hot-press solidifying, i.e. obtained polyphenylene oxide copper-clad plate.

Comparative example 3:

At room temperature, get Tao Shi 383 epoxy resin 50 ㎏, Bisphenol F benzoxazine resin 9 ㎏, phosphorus containing phenolic resin (Huizhou flourishing age reaches) 27 ㎏, silicon powder 26 ㎏, toluene 49 ㎏ and butanone 42 ㎏ join and join in glue tank, add imidazoles 1.5 ㎏, after stirring at room temperature 2h, under 171 DEG C of hot plates, circular hole method molding time is 269 seconds, namely completes the preparation of polyphenylene oxide sizing agent.

By glasscloth 2116 by adhesive applicator coating polyphenylene oxide sizing agent, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 70 DEG C ~ 165 DEG C, the speed of a motor vehicle (linear speed) of adhesive applicator is 2 ~ 10m/min, to the glasscloth of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, i.e. obtained prepreg.By superimposed for prepreg cut-parts, two-sidedly mix alligatoring Copper Foil, put on smooth stainless steel plate, be placed in vacuum press, with substantially not gummosis to be as the criterion increasing temperature and pressure gradually, finally when hot plate temperature pressure is 180 DEG C, 80 ㎏/cm ^2,time, after continuing 90min hot-press solidifying, i.e. obtained polyphenylene oxide copper-clad plate.

Thickness and the dielectric properties performance comparison situation of embodiment 1 ~ 8 and the polyphenylene oxide copper-clad plate obtained by comparative example 1 ~ 3 see the following form:

The thickness of polyphenylene oxide copper-clad plate in embodiment 1 ~ 8 and comparative example 1 ~ 3 and dielectric properties table

Upper table note: specific inductivity (Dk) and dielectric dissipation factor (Df) use Resonant-cavity Method (SPDR0) to measure.

Can see that the polyphenylene oxide sizing agent provided in the present invention can significantly improve the dielectric properties of copper clad laminate by upper table.

Embodiment 9:

A kind of polyphenylene oxide sizing agent, is mixed by the component raw material of resin combination 100 mass parts, powder body material 20 mass parts, curing catalyst 0.1 mass parts and solvent 50 mass parts and quality proportioning and forms;

Described resin combination is mixed by the component raw material of modified low molecular weight polyphenylene oxide resin 20 mass parts, epoxy resin 15 mass parts, benzoxazine colophony 20 mass parts, bimaleimide resin 3 mass parts and quality proportioning and forms;

The preparation method of described modified low molecular weight polyphenylene oxide resin is: first, add 100 mass parts polyphenylene oxide, 200 mass parts toluene in the reactor, be warming up to 80 DEG C and stir polyphenylene oxide particles is dissolved, add 12 mass parts diallyl bisphenols or tetraallyl dihydroxyphenyl propane again, be under the condition of 30 DEG C in temperature of reaction, drip with 0.5h or gradation add the peroxide initiator of 2.5 mass parts after, react stopped reaction after 1h again; The second, in reactor, add the alkali metal hydroxide of 1.4 mass parts and the phase-transfer catalyst of 1 mass parts, at the temperature of 40 DEG C, drip the chlorallylene of 18 mass parts, 0.5h drips off, and continues to react 8h at this temperature; 3rd, by the cut at (polyphenylene oxide resin of the allylation obtained) reaction soln Distillation recovery 60 DEG C, reclaim excessive chlorallylene, adding 18 mass parts mass percentage is the peroxide acetate aqueous solution of 40%, at 30 DEG C of temperature, carry out the reaction times is after 6h, stopped reaction, obtains modified polyphenylene ether resin reaction soln; Finally, the modified polyphenylene ether resin reaction soln deionized water obtained is extracted 3 times, each water consumption is 1/3rd of solvent toluene quality, extract rear combining extraction liquid, redistillation gone out most solvent toluene, again surplus solution is added drop-wise in 300 mass parts Methanol, namely modified polyphenylene ether resin can separate out, precipitation, filtration, and solids is again with after 50 mass parts Methanol/time washing 3 times, drying, i.e. obtained (grey powder) modified low molecular weight polyphenylene oxide resin.

Embodiment 10:

A kind of polyphenylene oxide sizing agent, is mixed by the component raw material of resin combination 100 mass parts, fire retardant 15 mass parts, powder body material 30 mass parts, curing catalyst 2 mass parts and solvent 100 mass parts and quality proportioning and forms;

Described resin combination is mixed by the component raw material of modified low molecular weight polyphenylene oxide resin 65 mass parts, epoxy resin 40 mass parts, benzoxazine colophony 40 mass parts, bimaleimide resin 9 mass parts and quality proportioning and forms;

The preparation method of described modified low molecular weight polyphenylene oxide resin is: first, add 100 mass parts polyphenylene oxide, 300 mass parts toluene in the reactor, be warming up to 90 DEG C and stir polyphenylene oxide particles is dissolved, add 20 mass parts diallyl bisphenols or tetraallyl dihydroxyphenyl propane again, be under the condition of 90 DEG C in temperature of reaction, drip with 0.5h or gradation add the peroxide initiator of 4 mass parts after, react stopped reaction after 10h again; The second, in reactor, add the alkali metal hydroxide of 2.2 mass parts and the phase-transfer catalyst of 2 mass parts, at the temperature of 70 DEG C, drip the chlorallylene of 30 mass parts, 1h drips off, and continues to react 10h at this temperature; 3rd, by the cut at (polyphenylene oxide resin of the allylation obtained) reaction soln Distillation recovery 60 DEG C, reclaim excessive chlorallylene, adding 30 mass parts mass percentage is the peroxide acetate aqueous solution of 40%, at 60 DEG C of temperature, carry out the reaction times is after 15h, stopped reaction, obtains modified polyphenylene ether resin reaction soln; Finally, the modified polyphenylene ether resin reaction soln deionized water obtained is extracted 3 times, each water consumption is 1/3rd of solvent toluene quality, extract rear combining extraction liquid, redistillation gone out most solvent toluene, again surplus solution is added drop-wise in 300 mass parts Methanol, namely modified polyphenylene ether resin can separate out, precipitation, filtration, and solids is again with after 50 mass parts Methanol/time washing 3 times, drying, i.e. obtained (grey powder) modified low molecular weight polyphenylene oxide resin.

Embodiment 11:

A kind of polyphenylene oxide sizing agent, is mixed by the component raw material of resin combination 100 mass parts, fire retardant 7 mass parts, powder body material 25 mass parts, curing catalyst 1 mass parts and solvent 75 mass parts and quality proportioning and forms;

Described resin combination is mixed by the component raw material of modified low molecular weight polyphenylene oxide resin 42 mass parts, epoxy resin 27 mass parts, benzoxazine colophony 30 mass parts, bimaleimide resin 6 mass parts and quality proportioning and forms;

The preparation method of described modified low molecular weight polyphenylene oxide resin is: first, add 100 mass parts polyphenylene oxide, 250 mass parts toluene in the reactor, be warming up to 85 DEG C and stir polyphenylene oxide particles is dissolved, add 16 mass parts diallyl bisphenols or tetraallyl dihydroxyphenyl propane again, be under the condition of 60 DEG C in temperature of reaction, drip with 0.5h or gradation add the peroxide initiator of 3.2 mass parts after, react stopped reaction after 5.5h again; The second, in reactor, add the alkali metal hydroxide of 1.8 mass parts and the phase-transfer catalyst of 1.5 mass parts, at the temperature of 55 DEG C, drip the chlorallylene of 24 mass parts, 0.8h drips off, and continues to react 9h at this temperature; 3rd, by the cut at (polyphenylene oxide resin of the allylation obtained) reaction soln Distillation recovery 60 DEG C, reclaim excessive chlorallylene, adding 24 mass parts mass percentage is the peroxide acetate aqueous solution of 40%, at 45 DEG C of temperature, carry out the reaction times is after 10h, stopped reaction, obtains modified polyphenylene ether resin reaction soln; Finally, the modified polyphenylene ether resin reaction soln deionized water obtained is extracted 3 times, each water consumption is 1/3rd of solvent toluene quality, extract rear combining extraction liquid, redistillation gone out most solvent toluene, again surplus solution is added drop-wise in 300 mass parts Methanol, namely modified polyphenylene ether resin can separate out, precipitation, filtration, and solids is again with after 50 mass parts Methanol/time washing 3 times, drying, i.e. obtained (grey powder) modified low molecular weight polyphenylene oxide resin.

Embodiment 12 ~ 18:

A kind of polyphenylene oxide sizing agent, is mixed by the component raw material of resin combination 100 mass parts, fire retardant 0 ~ 15 mass parts, powder body material 20 ~ 30 mass parts, curing catalyst 0.1 ~ 2 mass parts and solvent quality part and quality proportioning and forms;

Consumption (the unit: ㎏ of the mass parts) table of each component of polyphenylene oxide sizing agent in embodiment 12 ~ 18:

Consumption (the unit: ㎏ of the mass parts) table of each component of resin combination in embodiment 12 ~ 18:

The preparation method of described modified low molecular weight polyphenylene oxide resin is: first, add 100 mass parts polyphenylene oxide, 200 ~ 300 mass parts toluene in the reactor, be warming up to 80 ~ 90 DEG C and stir polyphenylene oxide particles is dissolved, add 12 ~ 20 mass parts diallyl bisphenols or tetraallyl dihydroxyphenyl propane again, be under the condition of 30 ~ 90 DEG C in temperature of reaction, drip with 0.5h or gradation add the peroxide initiator of 2.5 ~ 4 mass parts after, react stopped reaction after 1 ~ 10h again; Second, in reactor, add the alkali metal hydroxide of 1.4 ~ 2.2 mass parts and the phase-transfer catalyst of 1 ~ 2 mass parts, at the temperature of 40 ~ 70 DEG C, drip the chlorallylene of 18 ~ 30 mass parts, 0.5 ~ 1h drips off, and continues to react 8 ~ 10h at this temperature; 3rd, by the cut at (polyphenylene oxide resin of the allylation obtained) reaction soln Distillation recovery 60 DEG C, reclaim excessive chlorallylene, adding 18 ~ 30 mass parts mass percentage is the peroxide acetate aqueous solution of 40%, at 30 ~ 60 DEG C of temperature, carry out the reaction times is after 6 ~ 15h, stopped reaction, obtains modified polyphenylene ether resin reaction soln; Finally, the modified polyphenylene ether resin reaction soln deionized water obtained is extracted 3 times, each water consumption is 1/3rd of solvent toluene quality, extract rear combining extraction liquid, redistillation gone out most solvent toluene, again surplus solution is added drop-wise in 300 mass parts Methanol, namely modified polyphenylene ether resin can separate out, precipitation, filtration, and solids is again with after 50 mass parts Methanol/time washing 3 times, drying, i.e. obtained (grey powder) modified low molecular weight polyphenylene oxide resin.

Consumption (the unit: ㎏ of the mass parts) table of each component in the preparation method of embodiment 12 ~ 18 modified low molecular weight polyphenylene oxide resin:

Embodiment 19:

A preparation method for polyphenylene oxide sizing agent, has the following step:

A, prepare modified low molecular weight polyphenylene oxide resin, its preparation method is: first, add 100 mass parts polyphenylene oxide, 250 mass parts toluene in the reactor, be warming up to 86 DEG C and stir polyphenylene oxide particles is dissolved, add 16 mass parts diallyl bisphenols or tetraallyl dihydroxyphenyl propane again, be under the condition of 60 DEG C in temperature of reaction, drip with 0.5h or gradation add the peroxide initiator of 3 mass parts after, react stopped reaction after 5h again; The second, in reactor, add the alkali metal hydroxide of 1.8 mass parts and the phase-transfer catalyst of 1.5 mass parts, at the temperature of 50 DEG C, drip the chlorallylene of 24 mass parts, 0.7h drips off, and continues to react 9h at this temperature; 3rd, by the cut at (polyphenylene oxide resin of the allylation obtained) reaction soln Distillation recovery 60 DEG C, reclaim excessive chlorallylene, adding 24 mass parts mass percentage is the peroxide acetate aqueous solution of 40%, at 45 DEG C of temperature, carry out the reaction times is after 11h, stopped reaction, obtains modified polyphenylene ether resin reaction soln; Finally, the modified polyphenylene ether resin reaction soln deionized water obtained is extracted 3 times, each water consumption is 1/3rd of solvent toluene quality, extract rear combining extraction liquid, redistillation gone out most solvent toluene, again surplus solution is added drop-wise in 300 mass parts Methanol, namely modified polyphenylene ether resin can separate out, precipitation, filtration, and solids is again with after 50 mass parts Methanol/time washing 3 times, drying, i.e. obtained (grey powder) modified low molecular weight polyphenylene oxide resin;

B, prepare resin combination: get each component raw material, mixing composition resin combination by the component raw material of modified low molecular weight polyphenylene oxide resin 40 mass parts, epoxy resin 26 mass parts, benzoxazine colophony 30 mass parts, bimaleimide resin 7 mass parts and quality proportioning;

C, preparation polyphenylene oxide sizing agent:

Each component raw material is got by the component raw material of resin combination 100 mass parts, fire retardant 7 mass parts, powder body material 26 mass parts, curing catalyst 1.1 mass parts and solvent 70 mass parts and quality proportioning;

At room temperature, the resin combination of formula ratio, fire retardant, powder body material and solvent being joined joins in glue tank, stir 1.5h at the temperature of room temperature to 50 DEG C after, add the curing catalyst of formula ratio again, after continuing to stir 1.5h (to being uniformly dissolved), sampling detects, when under 171 DEG C of hot plates, circular hole method molding time is between 200 ~ 320 seconds, namely the preparation of polyphenylene oxide sizing agent is completed, obtained polyphenylene oxide sizing agent.

Embodiment 20:

B, prepare modified low molecular weight polyphenylene oxide resin, its preparation method is: first, add 100 mass parts polyphenylene oxide, 200 ~ 300 mass parts toluene in the reactor, be warming up to 80 ~ 90 DEG C and stir polyphenylene oxide particles is dissolved, add 12 ~ 20 mass parts diallyl bisphenols or tetraallyl dihydroxyphenyl propane again, be under the condition of 30 ~ 90 DEG C in temperature of reaction, drip with 0.5h or gradation add the peroxide initiator of 2.5 ~ 4 mass parts after, react stopped reaction after 1 ~ 10h again; Second, in reactor, add the alkali metal hydroxide of 1.4 ~ 2.2 mass parts and the phase-transfer catalyst of 1 ~ 2 mass parts, at the temperature of 40 ~ 70 DEG C, drip the chlorallylene of 18 ~ 30 mass parts, 0.5 ~ 1h drips off, and continues to react 8 ~ 10h at this temperature; 3rd, by the cut at (polyphenylene oxide resin of the allylation obtained) reaction soln Distillation recovery 60 DEG C, reclaim excessive chlorallylene, adding 18 ~ 30 mass parts mass percentage is the peroxide acetate aqueous solution of 40%, at 30 ~ 60 DEG C of temperature, carry out the reaction times is after 6 ~ 15h, stopped reaction, obtains modified polyphenylene ether resin reaction soln; Finally, the modified polyphenylene ether resin reaction soln deionized water obtained is extracted 3 times, each water consumption is 1/3rd of solvent toluene quality, extract rear combining extraction liquid, redistillation gone out most solvent toluene, again surplus solution is added drop-wise in 300 mass parts Methanol, namely modified polyphenylene ether resin can separate out, precipitation, filtration, and solids is again with after 50 mass parts Methanol/time washing 3 times, drying, i.e. obtained (grey powder) modified low molecular weight polyphenylene oxide resin; The concrete consumption of each component is with arbitrary in embodiment 9 ~ 18;

B, prepare resin combination: get each component raw material, mixing composition resin combination by the component raw material of modified low molecular weight polyphenylene oxide resin 20 ~ 65 mass parts, epoxy resin 15 ~ 40 mass parts, benzoxazine colophony 20 ~ 40 mass parts, bimaleimide resin 3 ~ 12 mass parts and quality proportioning; The concrete consumption of each component is with arbitrary in embodiment 9 ~ 18;

C, preparation polyphenylene oxide sizing agent:

Each component raw material is got by the component raw material of resin combination 100 mass parts, fire retardant 0 ~ 15 mass parts, powder body material 20 ~ 30 mass parts, curing catalyst 0.1 ~ 2 mass parts and solvent 50 ~ 100 mass parts and quality proportioning; The concrete consumption of each component is with arbitrary in embodiment 9 ~ 18;

At room temperature, the resin combination of formula ratio, fire retardant, powder body material and solvent being joined joins in glue tank, stir 1 ~ 2h at the temperature of room temperature to 50 DEG C after, add the curing catalyst of formula ratio again, after continuing stirring 1 ~ 2h (to being uniformly dissolved), sampling detects, when under 171 DEG C of hot plates, circular hole method molding time is between 200 ~ 320 seconds, namely the preparation of polyphenylene oxide sizing agent is completed, obtained polyphenylene oxide sizing agent.

Embodiment 21:

Polyphenylene oxide sizing agent is used for a preparation method for copper-clad plate, has the following step:

A, prepare polyphenylene oxide glasscloth prepreg:

Polyphenylene oxide sizing agent described in glasscloth 2116 is applied by adhesive applicator, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 70 DEG C, the speed of a motor vehicle (or claiming linear speed) of adhesive applicator is 10m/min, to the glasscloth 2116 of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, namely obtained polyphenylene oxide glasscloth prepreg, for subsequent use;

B, prepare copper-clad plate by prepreg:

Polyphenylene oxide glasscloth prepreg is cut into product desired size, by product desired thickness by one deck or two-layer above polyphenylene oxide glasscloth prepreg overlap, single or double mixes alligatoring Copper Foil, be placed on smooth stainless steel plate, be placed in vacuum press, (with substantially not gummosis be as the criterion) increasing temperature and pressure gradually, finally when hot plate temperature be 180 DEG C, pressure is 78 ㎏/cm ^2,time, determine to continue hot pressing time between 1 ~ 2h according to the thickness of sheet material, i.e. obtained polyphenylene oxide copper-clad plate.

Embodiment 22:

A, prepare polyphenylene oxide glasscloth prepreg:

Polyphenylene oxide sizing agent described in glasscloth 2116 is applied by adhesive applicator, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 165 DEG C, the speed of a motor vehicle (or claiming linear speed) of adhesive applicator is 2m/min, to the glasscloth 2116 of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, namely obtained polyphenylene oxide glasscloth prepreg, for subsequent use;

B, prepare copper-clad plate by prepreg:

Polyphenylene oxide glasscloth prepreg is cut into product desired size, by product desired thickness by one deck or two-layer above polyphenylene oxide glasscloth prepreg overlap, single or double mixes alligatoring Copper Foil, be placed on smooth stainless steel plate, be placed in vacuum press, (with substantially not gummosis be as the criterion) increasing temperature and pressure gradually, finally when hot plate temperature be 220 DEG C, pressure is 90 ㎏/cm ^2,time, determine to continue hot pressing time between 1 ~ 2h according to the thickness of sheet material, i.e. obtained polyphenylene oxide copper-clad plate.

Embodiment 23:

A, prepare polyphenylene oxide glasscloth prepreg:

Polyphenylene oxide sizing agent described in glasscloth 2116 is applied by adhesive applicator, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 115 DEG C, the speed of a motor vehicle (or claiming linear speed) of adhesive applicator is 6m/min, to the glasscloth 2116 of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, namely obtained polyphenylene oxide glasscloth prepreg, for subsequent use;

B, prepare copper-clad plate by prepreg:

Polyphenylene oxide glasscloth prepreg is cut into product desired size, by product desired thickness by one deck or two-layer above polyphenylene oxide glasscloth prepreg overlap, single or double mixes alligatoring Copper Foil, be placed on smooth stainless steel plate, be placed in vacuum press, (with substantially not gummosis be as the criterion) increasing temperature and pressure gradually, finally when hot plate temperature be 200 DEG C, pressure is 84 ㎏/cm ^2,time, determine to continue hot pressing time between 1 ~ 2h according to the thickness of sheet material, i.e. obtained polyphenylene oxide copper-clad plate.

In above-described embodiment 9 ~ 20: described epoxy resin can be bisphenol A type epoxy resin, brominated epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol aldehyde type epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, and containing one or more the mixture in the structural epoxy resins such as dipentadiene, aliphatics, phenyl ring, naphthalene nucleus, biphenyl;

In above-described embodiment 9 ~ 20: the structure of described epoxy resin and molecular weight do not have the requirement of specific, concrete, described epoxy resin preferred structure symmetry and epoxy equivalent (weight) are not more than the epoxy resin of 700, contribute to the compatible of each component like this, also contribute to the dipping of glasscloth;

In above-described embodiment 9 ~ 20: described benzoxazine colophony can be any one in phenol type benzoxazine colophony, bisphenol A-type benzoxazine colophony, bisphenol-f type benzoxazine colophony, bisphenol S type benzoxazine colophony, phenolic benzoxazine resin and two amine type benzoxazine colophonies;

In above-described embodiment 9 ~ 20: described fire retardant can be decabromodiphynly oxide, TDE, melamine polyphosphate, three (2,6-xylyl) phosphorus, 9,10-dihydro-9-oxy is mixed one or more the mixture in-10-phospho hetero phenanthrene-10-oxide compound (be called for short DOPO), 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (being called for short DOPO-DN), hexachlorocyclotriphosphazene, alkoxycyclotriphosphderivative, phenoxy group three phosphonitrile, phosphorus containing phenolic resin; Although modified low molecular weight polyphenylene oxide resin itself has certain flame retardant resistance, for fire-retardant there is high request time, also need to add certain above-mentioned fire retardant, the fire retardant of interpolation can be addition type, also can be response type.

In above-described embodiment 9 ~ 20: described powder body material can be one or more the composition in aluminium hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, silicon powder, talcum powder, zinc borate, mica, boron nitride;

In above-described embodiment 9 ~ 20: described curing catalyst can be one or more the composition in boron trifluoride ethylamine, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, triphenylphosphine, tributylphosphine, triethyl phosphine;

In above-described embodiment 9 ~ 20: described solvent can be one or more the mixture in toluene, dimethylbenzene, acetone, butanone;

In above-described embodiment 9 ~ 20: in the preparation method of described modified low molecular weight polyphenylene oxide resin:

Described phase-transfer catalyst is quaternary ammonium compound, can be one or more the composition in benzyltriethylammoinium chloride (being called for short TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate (being called for short TBAB), tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride.

In above-described embodiment: in the percentage adopted, do not indicate especially, be quality (weight) percentage; In the ratio adopted, do not indicate especially, be quality (weight) ratio; Described weight part can be all gram or kilogram.

In above-described embodiment: the processing parameter (temperature, time, concentration, pressure etc.) in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.

The concrete same prior art of technology contents described in content of the present invention and above-described embodiment, described starting material are commercially available prod.

The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.

Claims

1. a polyphenylene oxide sizing agent, is characterized in that: this polyphenylene oxide sizing agent is mixed by the component raw material of resin combination 100 mass parts, fire retardant 0 ~ 15 mass parts, powder body material 20 ~ 30 mass parts, curing catalyst 0.1 ~ 2 mass parts and solvent 50 ~ 100 mass parts and quality proportioning and forms; And at room temperature, be the glue between 200 ~ 320 seconds by above-mentioned material circular hole method molding time under joining glue tank to be made into 171 DEG C of hot plates, i.e. polyphenylene oxide sizing agent;

Described epoxy resin is containing one or more the mixture in dipentadiene, aliphatics, phenyl ring, naphthalene ring epoxy resin;

Described benzoxazine colophony is any one in phenol type benzoxazine colophony, bisphenol A-type benzoxazine colophony, bisphenol-f type benzoxazine colophony, bisphenol S type benzoxazine colophony, phenolic benzoxazine resin and two amine type benzoxazine colophonies;

Described fire retardant is decabromodiphynly oxide, TDE, melamine polyphosphate, three (2,6-xylyl) phosphorus, 9,10-dihydro-9-oxy is mixed one or more the mixture in-10-phospho hetero phenanthrene-10-oxide compound, 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, hexachlorocyclotriphosphazene, alkoxycyclotriphosphderivative, phenoxy group three phosphonitrile, phosphorus containing phenolic resin;

Described powder body material is one or more the composition in aluminium hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, silicon powder, talcum powder, zinc borate, mica, boron nitride;

Described curing catalyst is one or more the composition in boron trifluoride ethylamine, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, triphenylphosphine, tributylphosphine, triethyl phosphine;

Described solvent is one or more the mixture in toluene, dimethylbenzene, acetone, butanone;

The preparation method of described modified low molecular weight polyphenylene oxide resin is: first, add 100 mass parts polyphenylene oxide, 200 ~ 300 mass parts toluene in the reactor, be warming up to 80 ~ 90 DEG C and stir polyphenylene oxide particles is dissolved, add 12 ~ 20 mass parts diallyl bisphenols or tetraallyl dihydroxyphenyl propane again, be under the condition of 30 ~ 90 DEG C in temperature of reaction, drip with 0.5h or gradation add the peroxide initiator of 2.5 ~ 4 mass parts after, react stopped reaction after 1 ~ 10h again; Second, in reactor, add the alkali metal hydroxide of 1.4 ~ 2.2 mass parts and the phase-transfer catalyst of 1 ~ 2 mass parts, at the temperature of 40 ~ 70 DEG C, drip the chlorallylene of 18 ~ 30 mass parts, 0.5 ~ 1h drips off, and continues to react 8 ~ 10h at this temperature; 3rd, by the cut at reaction soln Distillation recovery 60 DEG C, reclaim excessive chlorallylene, adding 18 ~ 30 mass parts mass percentage is the peroxide acetate aqueous solution of 40%, at 30 ~ 60 DEG C of temperature, carry out the reaction times is after 6 ~ 15h, stopped reaction, obtains modified polyphenylene ether resin reaction soln; Finally, the modified polyphenylene ether resin reaction soln deionized water obtained is extracted 3 times, each water consumption is 1/3rd of solvent toluene quality, extract rear combining extraction liquid, redistillation gone out most solvent toluene, again surplus solution is added drop-wise in 300 mass parts Methanol, namely modified polyphenylene ether resin can separate out, precipitation, filtration, and solids is again with after 50 mass parts Methanol/time washing 3 times, drying, i.e. obtained modified low molecular weight polyphenylene oxide resin;

Described polyphenylene oxide is poly-2,6-dimethyl-Isosorbide-5-Nitrae-phenylate;

Described initiator is one or more the composition in benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, peroxidation trimethylacetic acid tertiary butyl ester, methylethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate;

Described alkali metal hydroxide is one or more the mixture in lithium hydroxide, sodium hydroxide, potassium hydroxide;

Described phase-transfer catalyst is one or more the composition in benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride;

2., by the preparation method of polyphenylene oxide sizing agent described in claim 1, it is characterized in that there is the following step:

A, prepare modified low molecular weight polyphenylene oxide resin, its preparation method is: first, add 100 mass parts polyphenylene oxide, 200 ~ 300 mass parts toluene in the reactor, be warming up to 80 ~ 90 DEG C and stir polyphenylene oxide particles is dissolved, add 12 ~ 20 mass parts diallyl bisphenols or tetraallyl dihydroxyphenyl propane again, be under the condition of 30 ~ 90 DEG C in temperature of reaction, drip with 0.5h or gradation add the peroxide initiator of 2.5 ~ 4 mass parts after, react stopped reaction after 1 ~ 10h again; Second, in reactor, add the alkali metal hydroxide of 1.4 ~ 2.2 mass parts and the phase-transfer catalyst of 1 ~ 2 mass parts, at the temperature of 40 ~ 70 DEG C, drip the chlorallylene of 18 ~ 30 mass parts, 0.5 ~ 1h drips off, and continues to react 8 ~ 10h at this temperature; 3rd, by the cut at reaction soln Distillation recovery 60 DEG C, reclaim excessive chlorallylene, adding 18 ~ 30 mass parts mass percentage is the peroxide acetate aqueous solution of 40%, at 30 ~ 60 DEG C of temperature, carry out the reaction times is after 6 ~ 15h, stopped reaction, obtains modified polyphenylene ether resin reaction soln; Finally, the modified polyphenylene ether resin reaction soln deionized water obtained is extracted 3 times, each water consumption is 1/3rd of solvent toluene quality, extract rear combining extraction liquid, redistillation gone out most solvent toluene, again surplus solution is added drop-wise in 300 mass parts Methanol, namely modified polyphenylene ether resin can separate out, precipitation, filtration, and solids is again with after 50 mass parts Methanol/time washing 3 times, drying, i.e. obtained modified low molecular weight polyphenylene oxide resin;

B, prepare resin combination: get each component raw material, mixing composition resin combination by the component raw material of modified low molecular weight polyphenylene oxide resin 20 ~ 65 mass parts, epoxy resin 15 ~ 40 mass parts, benzoxazine colophony 20 ~ 40 mass parts, bimaleimide resin 3 ~ 9 mass parts and quality proportioning;

C, preparation polyphenylene oxide sizing agent:

At room temperature, the resin combination of formula ratio, fire retardant, powder body material and solvent being joined joins in glue tank, stir 1 ~ 2h at the temperature of room temperature to 50 DEG C after, add the curing catalyst of formula ratio again, after continuing stirring 1 ~ 2h, sampling detects, when under 171 DEG C of hot plates, circular hole method molding time is between 200 ~ 320 seconds, namely the preparation of polyphenylene oxide sizing agent is completed, obtained polyphenylene oxide sizing agent;

Described solvent is one or more the mixture in toluene, dimethylbenzene, acetone, butanone.

3. adopt polyphenylene oxide sizing agent described in claim 1 to prepare the method for copper-clad plate, it is characterized in that there is the following step:

A, prepare polyphenylene oxide sizing agent according to claim 1 by polyphenylene oxide sizing agent preparation method according to claim 2, for subsequent use;

B, prepare polyphenylene oxide glasscloth prepreg:

Polyphenylene oxide sizing agent described in glasscloth 2116 is applied by adhesive applicator, the drying tunnel length of described adhesive applicator is 24m, is divided into 3 sections, every section 8m, the scope of stoving temperature point gradient is 70 DEG C ~ 165 DEG C, the speed of a motor vehicle of adhesive applicator is 2 ~ 10m/min, to the glasscloth 2116 of described polyphenylene oxide sizing agent be coated with after the drying tunnel of described adhesive applicator cures, namely obtained polyphenylene oxide glasscloth prepreg, for subsequent use;

C, prepare copper-clad plate by prepreg:

Polyphenylene oxide glasscloth prepreg is cut into product desired size, by product desired thickness by one deck or two-layer above polyphenylene oxide glasscloth prepreg overlap, single or double mixes alligatoring Copper Foil, be placed on smooth stainless steel plate, be placed in vacuum press, increasing temperature and pressure gradually, finally when hot plate temperature be 180 ~ 220 DEG C, pressure is 78 ~ 90 ㎏/cm ²time, determine to continue hot pressing time between 1 ~ 2h according to the thickness of sheet material, i.e. obtained polyphenylene oxide copper-clad plate.