CN110423342B - Organic silicon modified polyphenyl ether resin and preparation method and application thereof - Google Patents
Organic silicon modified polyphenyl ether resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN110423342B CN110423342B CN201910638310.9A CN201910638310A CN110423342B CN 110423342 B CN110423342 B CN 110423342B CN 201910638310 A CN201910638310 A CN 201910638310A CN 110423342 B CN110423342 B CN 110423342B
- Authority
- CN
- China
- Prior art keywords
- resin
- polyphenylene ether
- resin composition
- ether resin
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
-
- 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
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides an organic silicon modified polyphenyl ether resin and a preparation method and application thereof, wherein the polyphenyl ether resin has the following structure:
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to organic silicon modified polyphenyl ether resin and a preparation method and application thereof.
Background
With the development of electronic technology, particularly fifth generation mobile communication technology, the demand for high-frequency and high-speed insulating materials is increasing. The high-performance insulating material is widely applied to the fields of copper-clad plates, antennas and the like, and is required to have higher glass transition temperature, lower dielectric constant, lower dielectric loss, lower thermal expansion coefficient, lower water absorption and better processing performance.
At present, epoxy resin, phenolic resin and the like are commonly used as insulating and bonding resin in the field of copper clad plates, although the resin has better processing performance and processing technology, the resin also has the great defect that Dk/Df (dielectric constant and dielectric loss factor) is large and is not suitable for being used in high-frequency and high-speed circuits. Some technicians apply low Dk/Df materials to high-frequency and high-speed copper-clad plates, wherein common materials include hydrocarbon resin, polytetrafluoroethylene, polyimide, styrene-maleic anhydride copolymer, cyanate ester, polyphenyl ether, active ester, liquid crystal resin and the like. Wherein, the polyphenyl ether has higher glass transition temperature, lower Dk/Df and lower water absorption, and can be widely applied to the field of high-frequency and high-speed electronics.
At present, most of synthesized polyphenyl ether resin is hydroxyl-terminated resin, the hydroxyl reaction activity is low, the reaction groups are few, and a curing system with high crosslinking density cannot be formed, so that the mechanical property, the thermal stability, the adhesive force and other properties are greatly influenced. In order to obtain better performance, modification of polyphenylene ether resins is often required. The prior art discloses a method for purifying capped polyphenylene ether, which relates to a relatively complex phase separation process and is complex to operate. In the field of siloxane-based modified polyphenylene oxide resin, the prior art discloses a method for obtaining styrene-based siloxane-based polyphenylene oxide resin by reacting chlorosilane, polyphenylene oxide and hydroxystyrene, and the method uses halogen and has higher requirements on processes and equipment. The prior art also discloses a method for preparing silicon-containing dihydroxy polyphenyl ether by modifying organic silicon, wherein the modified polyphenyl ether still takes hydroxyl as a curing group, and the reaction activity of the modified polyphenyl ether is not obviously improved, so that the requirements of the material in practical application cannot be met.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an organic silicon modified polyphenyl ether resin and a preparation method and application thereof.
To achieve the above object, a first aspect of the present invention provides a silicone-modified polyphenylene ether resin having a structure of formula a:
wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 are each independently selected from hydrogen, linear or branched C1-C6 alkyl, C6-C12 aryl substituted or unsubstituted with linear or branched C1-C4 alkyl, C1-C6 haloalkyl, aminoalkyl, alkoxy, cyano and vinyl, R13, R14 and R15 are each independently selected from hydrogen, linear or branched C1-C8 alkyl, C1-C8 alkoxy, C36 1-C4 alkyl substituted or unsubstituted C6 aryl, C6-C6 haloalkyl, aminoalkyl, cyano, vinyl, epoxy and C6-C6 alkyl substituted with olefinic bond, acryloxy, acrylic acid or anhydride;
n is 2 to 200.
The invention provides a preparation method of the polyphenylene ether resin, which comprises the steps of reacting hydroxyl-terminated polyphenylene ether with organic siloxane to obtain the polyphenylene ether resin shown in the structure of the formula A;
the hydroxy-terminated polyphenylene ether has the structure of formula B:
in the formula B, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 are all independently selected from hydrogen, linear or branched C1-C6 alkyl, C6-C12 aryl substituted or not by linear or branched C1-C4 alkyl, C1-C6 haloalkyl, aminoalkyl, alkoxy, cyano and vinyl; n is 2 to 200;
the organosiloxane has the structure of formula C:
in the formula C, R16 is a straight chain or branched chain C1-C6 alkyl; r13, R14 and R15 are each independently selected from hydrogen, linear or branched C1-C8 alkyl, C1-C8 alkoxy, C6-C12 aryl substituted or unsubstituted with linear or branched C1-C4 alkyl, C1-C8 haloalkyl, aminoalkyl, cyano, vinyl, epoxy and C1-C8 alkyl substituted with olefinic bond, acryloxy, acrylic acid or anhydride.
As a further improvement of the technical proposal, the organic siloxane comprises any one of vinyl trimethoxy silane, vinyl triethoxy silane, P-styrene trimethoxy silane, N-2- (aminoethyl) -3-aminopropyl methyl dimethoxy silane, N-2- (aminoethyl) -3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3-acrylic propyl trimethoxy silane, 3- (methacryloyloxy) propyl trimethoxy silane and (3-triethoxysilyl) succinic anhydride.
As a further improvement of the above technical solution, the reaction of the hydroxy-terminated polyphenylene ether and the organosiloxane is carried out in an organic solvent, wherein the organic solvent comprises one or more of alkanes, ketones, ethers, esters and amides;
preferably, the organic solvent comprises one or more of toluene, xylene, trimethylbenzene, cyclohexanone, methyl isobutyl ketone, N-dimethylformamide, tetrahydrofuran, butyl acetate and petroleum ether.
As a further improvement of the above technical scheme, the preparation method further comprises adding a catalyst into a reaction system of the reaction of the hydroxyl-terminated polyphenylene ether and the organosiloxane;
preferably, the catalyst comprises one or more of an acid catalyst, a base catalyst, a metal compound catalyst and an ester catalyst;
preferably, the catalyst comprises one or more of sulfuric acid, phosphoric acid, hydrochloric acid, oxalic acid, acetic acid, activated clay, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, sodium ethoxide, lithium acetylacetonate, dibutyltin oxide, tetramethyl titanate, tetrabutyl titanate, calcium oxide, aluminum oxide, and magnesium oxide.
As a further improvement of the above technical solution, after the reaction of the hydroxyl-terminated polyphenylene ether with the organosiloxane is completed, removing impurities from the solution after the reaction is completed to obtain the polyphenylene ether resin;
preferably, the impurity removal method adopts one or more of inert gas purging, reduced pressure distillation and high temperature distillation.
As a further improvement of the technical scheme, the molar ratio of the hydroxyl-terminated polyphenylene oxide to the organic siloxane is 1: 0.1-2.
As a further improvement of the technical proposal, the usage amount of the organic solvent is not more than 4 times of the usage amount of the hydroxyl-terminated polyphenylene ether in parts by mass.
As a further improvement of the above technical scheme, the usage amount of the catalyst is not more than 5% of the usage amount of the hydroxy-terminated polyphenylene ether in parts by mass.
The third aspect of the present invention provides a resin composition comprising the polyphenylene ether resin as described above;
preferably, the resin composition further comprises an epoxy resin and/or a resin having a double bond;
preferably, the epoxy resin comprises one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, brominated epoxy resin, and phosphorus-containing epoxy resin.
Preferably, the resin with double bonds comprises one or more of styrene-butadiene copolymer, polybutadiene and styrene-butadiene-divinylbenzene copolymer;
preferably, the styrene-butadiene copolymer, polybutadiene, styrene-butadiene-divinylbenzene copolymer may each be independently modified with an amino group, maleic anhydride, epoxy group, acrylate, hydroxyl group or carboxyl group;
preferably, the resin composition further includes an inorganic filler;
preferably, the resin composition further comprises a flame retardant;
preferably, the resin composition further comprises a glue solvent;
preferably, the resin composition further comprises a curing catalyst;
preferably, the resin composition further comprises an initiator.
In a fourth aspect, the present invention provides a prepreg comprising a reinforcing material, and the resin composition as described above attached to the reinforcing material by dip drying.
A fifth aspect of the invention provides a laminate comprising a prepreg as described above.
A sixth aspect of the present invention provides a printed circuit board including the prepreg as described above.
The invention has the beneficial effects that:
the invention provides an organic silicon modified polyphenyl ether resin and a preparation method and application thereof, wherein the polyphenyl ether resin is prepared by introducing organic siloxane into hydroxyl-terminated polyphenyl ether, so that the polyphenyl ether resin has better reactivity, crosslinking density, dielectric property, impact resistance and heat resistance through introducing various reactive functional groups into organic silicon branched chains. And the polyphenyl ether resin is suitable for manufacturing finished products such as copper clad laminates, laminated boards, printed circuit boards and the like, and when the polyphenyl ether resin is used for manufacturing the copper clad laminates, the laminated boards and the printed circuit boards, the manufactured finished products have excellent dielectric properties and good heat resistance, impact resistance, flame retardance and processability.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention.
FIG. 1 is a GPC chart of a hydroxy-terminated polyphenylene ether in example 3 of the invention;
FIG. 2 is a GPC chart of the polyphenylene ether resin of example 3 of the invention.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
The invention provides an organosilicon modified polyphenylene ether resin, which has a structure shown in a formula A:
wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 are each independently selected from hydrogen, linear or branched C1-C6 alkyl, C6-C12 aryl substituted or unsubstituted with linear or branched C1-C4 alkyl, C1-C6 haloalkyl, aminoalkyl, alkoxy, cyano and vinyl, R13, R14 and R15 are each independently selected from hydrogen, linear or branched C1-C8 alkyl, C1-C8 alkoxy, C36 1-C4 alkyl substituted or unsubstituted C6 aryl, C6-C6 haloalkyl, aminoalkyl, cyano, vinyl, epoxy and C6-C6 alkyl substituted with olefinic bond, acryloxy, acrylic acid or anhydride;
n is 2 to 200.
It is understood that the polyphenylene ether resin obtained by introducing the organosiloxane into the hydroxyl-terminated polyphenylene ether in the present embodiment can have better reactivity, crosslinking density, dielectric properties and impact and heat resistance by introducing various reactive functional groups into the silicone side chain. The polyphenyl ether resin is suitable for manufacturing finished products such as copper clad laminates, laminated boards, printed circuit boards and the like, and when the polyphenyl ether resin is used for manufacturing the copper clad laminates, the laminated boards and the printed circuit boards, the manufactured finished products have excellent dielectric properties and good heat resistance, impact resistance, flame retardance and processability. Can meet the application requirements of products such as high-frequency and high-speed copper clad plates and the like.
The invention also provides a preparation method of the organic silicon modified polyphenyl ether resin, which comprises the steps of reacting double-end hydroxyl polyphenyl ether with organic siloxane to obtain polyphenyl ether resin shown in the structure of the formula A;
the hydroxy-terminated polyphenylene ether has the structure of formula B:
in the formula B, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 are all independently selected from hydrogen, linear or branched C1-C6 alkyl, C6-C12 aryl substituted or not by linear or branched C1-C4 alkyl, C1-C6 haloalkyl, aminoalkyl, alkoxy, cyano and vinyl; n is 2 to 200;
the organosiloxane has the structure of formula C:
in the formula C, R16 is a straight chain or branched chain C1-C6 alkyl; r13, R14 and R15 are each independently selected from hydrogen, linear or branched C1-C8 alkyl, C1-C8 alkoxy, C6-C12 aryl substituted or unsubstituted with linear or branched C1-C4 alkyl, C1-C8 haloalkyl, aminoalkyl, cyano, vinyl, epoxy, C1-C8 alkyl substituted with olefinic bond, acryloxy, acrylic acid and anhydride;
the reaction formula is as follows:
preferably, the organosiloxane comprises any one of vinyltrimethoxysilane, vinyltriethoxysilane, P-styrenetrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-propenoic propyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane and (3-triethoxysilylpropyl) succinic anhydride.
Preferably, the molar ratio of the hydroxyl-terminated polyphenylene ether to the organosiloxane is 1:0.1-2, and may be, for example, 1:0.1, 1:0.5, 1:1, 1:1.2, 1:1.5, 1:2, and the like.
As a specific embodiment, the hydroxyl-terminated polyphenylene ether and the organosiloxane can be directly reacted to obtain the polyphenylene ether resin shown in the structure of the formula A.
Of course, as another specific embodiment, the reaction of the hydroxy-terminated polyphenylene ether and the organosiloxane may be carried out in an organic solvent including one or more of alkanes, ketones, ethers, esters, amides.
The specific operation is as follows: firstly, dissolving the hydroxyl-terminated polyphenyl ether in an organic solvent, and then adding organic siloxane for reaction.
In the present embodiment, the organic solvent can favorably dissolve the bishydroxyphenylene ether to form a homogeneous system, and the reaction of the bishydroxyphenylene ether with the organosiloxane can proceed smoothly.
The organic solvent includes but is not limited to one or more of toluene, xylene, trimethylbenzene, cyclohexanone, methyl isobutyl ketone, N-dimethylformamide, tetrahydrofuran, butyl acetate and petroleum ether.
The amount of the organic solvent used is not more than 4 times, for example, 0.1 time, 0.5 time, 1 time, 2 times, 3 times, 4 times, etc., the amount of the above-mentioned bishydroxyphenylene ether in parts by mass.
Preferably, the amount of the organic solvent used is 0.2 to 2 times the amount of the bishydroxyphenylene ether used.
In order to further accelerate the reaction rate of the hydroxyl terminated polyphenylene ether and the organic siloxane, as an implementation mode, the method also comprises adding a catalyst into a reaction system for reacting the hydroxyl terminated polyphenylene ether and the organic siloxane.
Preferably, the catalyst comprises one or more of an acid catalyst, a base catalyst, a metal compound catalyst and an ester catalyst;
the catalyst includes, but is not limited to, one or more of sulfuric acid, phosphoric acid, hydrochloric acid, oxalic acid, acetic acid, activated clay, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, sodium ethoxide, lithium acetylacetonate, dibutyltin oxide, tetramethyl titanate, tetrabutyl titanate, calcium oxide, aluminum oxide, and magnesium oxide.
The amount of the catalyst used is not more than 5% by mass of the amount of the bishydroxyphenylene ether, and may be, for example, 0.1%, 1%, 2%, 3%, 4%, 5%, etc.
As a specific embodiment, the preparation method of the silicone modified polyphenylene ether resin comprises the following steps: adding hydroxyl-terminated polyphenyl ether and a catalyst into an organic solvent, stirring and heating, then adding organic siloxane for reaction, and obtaining the polyphenyl ether resin shown in the structure of the formula A after the reaction is finished.
In the preparation method of the organic silicon modified polyphenylene ether resin, the reaction temperature is not particularly limited, and is preferably between 80 ℃ and 180 ℃, for example, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃ and the like can be realized, and more preferably 100-;
the reaction time is suitably set according to the selected reaction temperature and the amount of the catalyst, and is preferably 0.5h to 20h, for example, 0.5h, 1h, 2h, 5h, 7h, 8h, 10h, 12h, 15h, 18h, 20h, etc., more preferably 2 to 12h, and still more preferably 5 to 10 h.
It is understood that in the reaction process of the hydroxyl terminated polyphenylene ether and the organosiloxane, the specific operation is to add the organosiloxane into the hydroxyl terminated polyphenylene ether, the mode of adding the organosiloxane is not particularly specified, the mode of adding the organosiloxane rapidly or dropwise can be adopted, and the adding time can be between 1min and 360min, such as 1min, 30min, 60min, 90min, 100min, 150min, 200min, 250min, 300min, 360min and the like.
Similarly, the reaction environment of the reaction system is not particularly limited, and the reaction can be carried out in air. Preferably, inert gas such as nitrogen is filled into the reaction system for protection in order to isolate water vapor and the like.
Specifically, after the reaction of the hydroxyl-terminated polyphenylene oxide and the organosiloxane is completed, removing impurities from the solution after the reaction is completed to obtain the polyphenylene oxide resin;
preferably, the method for removing impurities may employ one or more of inert gas purging, reduced pressure distillation and high temperature distillation.
More preferably, the method for removing impurities is any one of reduced pressure distillation or high temperature distillation;
the pressure is not particularly limited in the vacuum distillation, but is preferably 30 to 101.325kPa, and may be, for example, 30kPa, 50kPa, 70kPa, 100kPa, 101.325kPa, or the like;
for high temperature distillation, the distillation temperature is between 80-250 deg.C, such as 80 deg.C, 100 deg.C, 130 deg.C, 150 deg.C, 170 deg.C, 200 deg.C, 230 deg.C, 250 deg.C, etc.
It is understood that by performing the above-described operation of removing impurities from the solution after completion of the reaction, the alcohol obtained by the reaction, the added organic solvent, and the like can be removed, thereby obtaining a finished polyphenylene ether resin.
The present invention also provides a resin composition comprising the silicone-modified polyphenylene ether resin as described above.
Preferably, the resin composition further comprises an epoxy resin and/or a resin having a double bond;
it is understood that in the resin composition, when the polyphenylene ether resin has a double bond, it can be cured by itself radical to form a cured resin; of course, in other embodiments, resins with double bonds other than the polyphenylene ether resin of formula a may be added to promote curing.
When the polyphenylene ether resin is an amino group or an acid anhydride functional group, the resin composition further needs to include an epoxy resin other than the polyphenylene ether resin having the structure of formula a for co-curing, wherein the amount of the epoxy resin and the polyphenylene ether resin is not particularly limited, and is preferably: when the polyphenylene ether resin is an amino functional group, the amount of the epoxy group is 0.7-2 times that of the amino group; when the polyphenyl ether resin is an anhydride functional group, the using amount of the epoxy group is 0.8-1.5 times of that of the anhydride; of course, in the above resin composition, a resin having a double bond may be further added for co-curing, and the amount thereof is not particularly limited.
Preferably, the epoxy resin comprises one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, brominated epoxy resin and phosphorus-containing epoxy resin; of course, in other embodiments, the epoxy resin may also include one or more of a modified bisphenol a epoxy resin, a modified bisphenol F epoxy resin, a modified bisphenol S epoxy resin, a modified phenol novolac epoxy resin, a modified o-cresol novolac epoxy resin, a modified biphenyl epoxy resin, a modified dicyclopentadiene epoxy resin, a modified brominated epoxy resin, and a modified phosphorous epoxy resin.
Preferably, the resin with double bonds comprises one or more of styrene-butadiene copolymer, polybutadiene and styrene-butadiene-divinylbenzene copolymer;
preferably, the styrene-butadiene copolymer, polybutadiene and styrene-butadiene-divinylbenzene copolymer may each be independently modified with an amino group, maleic anhydride, epoxy group, acrylate, hydroxyl group or carboxyl group;
preferably, the resin composition further includes an inorganic filler;
preferably, the inorganic filler comprises one or more of aluminum hydroxide, boehmite, silica, talc, mica, barium sulfate, lithopone, calcium carbonate, wollastonite, kaolin, brucite, diatomaceous earth, bentonite, and pumice;
preferably, the resin composition further comprises a flame retardant;
preferably, the flame retardant comprises an inorganic flame retardant and/or an organic flame retardant;
preferably, the organic flame retardant comprises one or more of tris (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphinobenzene, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a phenoxyphosphazene compound, a nitrogen-phosphorus intumescent organic flame retardant, a phosphorus-containing phenolic resin and phosphorus-containing bismaleimide;
preferably, the inorganic flame retardant comprises one or more of zinc borate, aluminum hydroxide, magnesium hydroxide and antimony oxide.
Preferably, the resin composition further comprises a curing catalyst;
preferably, the curing catalyst comprises an imidazole catalyst and/or a tertiary amine catalyst;
preferably, the curing catalyst comprises one or more of 2-methylimidazole, 2-phenylimidazole, benzyldimethylamine, triethylamine, triethanolamine, dimethylethanolamine and triphenylphosphine;
preferably, the resin composition further comprises an initiator;
preferably, the initiator comprises an organic peroxide;
preferably, the initiator comprises one or more of methyl ethyl ketone peroxide, benzoyl peroxide, cumene peroxide and tert-butyl hydroperoxide;
preferably, the resin composition further comprises a glue solvent, and the resin composition can form a glue solution by adding the glue solvent.
Preferably, the glue solvent comprises one or more of ketones, ethers, alcohols, lipids and aromatic hydrocarbons;
preferably, the glue solvent comprises one or more of acetone, butanone, cyclohexanone, methyl isobutyl ketone, ethylene glycol methyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide or N-methyl-2-pyrrolidone, toluene, xylene, butanol, ethyl acetate and butyl acetate;
the invention also provides a prepreg, which comprises a reinforcing material and the resin composition attached to the reinforcing material after impregnation and drying.
Preferably, the reinforcing material includes carbon fiber, glass fiber cloth, aramid fiber, or the like.
The invention also provides a laminate comprising a prepreg as described above.
The invention also provides a printed circuit board which comprises the prepreg.
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
300g of xylene (national medicine) was charged into a 1L four-neck flask equipped with a stirrer, a thermocouple, a reflux condenser, an oil-water separator and a dropping funnel, stirring was started, 466g (0.29mol) of double-terminal hydroxyl-group polyphenylene ether (SA90, SABIC Co.) was added in portions under nitrogen protection, the temperature was raised to 100 ℃ and stirred until dissolved, the temperature was further raised to 130 ℃ and 0.1g of tetrabutyl titanate (AR, Unionmelt reagent) was added, 40g (0.19mol) of N-aminoethyl-3-aminopropylmethyldimethoxysilane (KBM602, Japan Xin) was dropped into the flask using the dropping funnel, the temperature was maintained at 130 ℃ for 5 hours, and methanol and xylene were removed by reduced pressure distillation to obtain a bisaminosilane-modified polyphenylene ether resin, which was designated as resin A.
Example 2
300g of N, N-dimethylformamide (a traditional Chinese medicine) is added into a 1L four-neck flask with a stirrer, a thermocouple, a reflux condenser tube, an oil-water separator and a dropping funnel, stirring is started, nitrogen is introduced for protection, 384g (0.24mol) of hydroxyl-terminated polyphenylene oxide (SA90, SABIC company) is added in batches, stirring is carried out until the hydroxyl-terminated polyphenylene oxide is dissolved, the temperature is continuously increased to 130 ℃, 131g (0.43mol) of 3- (triethoxysilyl) propyl succinic anhydride (GF20, Wacker chemical) is dropped into the flask by using the dropping funnel, the temperature is kept at 130 ℃ for 6 hours, simultaneously methanol and N, N-dimethylformamide are removed by reduced pressure distillation, and the flask is dried for 3 hours at 160 ℃ to obtain the polyphenylene oxide resin with the silane modified by the anhydride at the two ends, which is marked as resin B.
Example 3
Adding 200g of xylene (traditional Chinese medicine) into a 1L four-neck flask with a stirrer, a thermocouple, a reflux condenser tube, an oil-water separator and a dropping funnel, starting stirring, introducing nitrogen for protection, adding 406g (0.25mol) of hydroxyl-terminated polyphenylene oxide (SA90, SABIC company) in batches, heating to 100 ℃, stirring until the mixture is dissolved, continuously heating to 130 ℃, adding 1.0g of phosphoric acid (traditional Chinese medicine), dropping 60g (0.40mol) of vinyl trimethoxy silane (KBM1003, Japan shines) by using the dropping funnel, preserving heat at 130 ℃ for 6 hours, and simultaneously removing methanol and xylene by reduced pressure distillation to obtain the divinyl silane modified polyphenylene oxide resin which is marked as resin C;
referring to FIG. 1, the GPC chart of the double hydroxyl-terminated polyphenylene ether (SA90) of this example found that the number average molecular weight (Mn) was 2504 and the weight average molecular weight (Mw) was 5104; referring to FIG. 2, the prepared polyphenylene ether resin (resin C) had a GPC chart, and found that the number average molecular weight (Mn) was 3146 and the weight average molecular weight (Mw) was 8184; from this, it was found that this bishydroxyphenylene ether had a chain extension reaction with vinyltrimethoxysilane to give a polyphenylene ether resin (resin C) having a number average molecular weight of 3146 and a weight average molecular weight of 8184.
Example 4
300g of xylene (a traditional Chinese medicine) is added into a 1L four-neck flask with a stirrer, a thermocouple, a reflux condenser tube, an oil-water separator and a dropping funnel, stirring is started, nitrogen protection is introduced, 415g (0.26mol) of hydroxyl-terminated polyphenylene oxide (SA90, SABIC company) is added in batches, the temperature is raised to 100 ℃, stirring is carried out until the hydroxyl-terminated polyphenylene oxide is dissolved, the temperature is raised to 130 ℃, 1.0g of acid clay (Focus chemical) is added, 102g (0.41mol) of 3- (methacryloyloxy) propyl trimethoxy silane (KBM5103, Japan Xinyue) is dripped by using the dropping funnel, the temperature is kept at 130 ℃ for 6 hours, and methanol and xylene are removed by reduced pressure distillation to obtain the polyphenylene oxide resin modified by methacrylate silane, which is marked as resin D.
Application example 1
100g of the polyphenylene ether resin A obtained in example one, 35g of dicyclopentadiene epoxy resin (NPPN272H, south Asia plastic) and 45g of fused silica were each dissolved in butanone solvent, and then mixed uniformly and adjusted to a suitable viscosity to form a dope.
Soaking 2116 glass cloth in the glue solution, drying the glass cloth to remove butanone to obtain a prepreg, and pressing and curing 8 layers of the prepreg at 180 ℃ for 2 hours to obtain a copper-clad plate with the thickness of 0.9-1.1mm, wherein the properties of the copper-clad plate are shown in the table I.
Application example 2
150g of polyphenylene ether resin A obtained in example I, 7g of PMDA (curing agent, chemical industry constant) and 45g of fused silica were dissolved in butanone solvent, and then mixed uniformly and adjusted to a suitable viscosity to form a glue solution.
Soaking 2116 glass cloth in the glue solution, drying the glass cloth to remove butanone to obtain a prepreg, and pressing and curing 8 layers of the prepreg at 220 ℃ for 3 hours to obtain a copper-clad plate with the thickness of 0.9-1.1mm, wherein the properties of the copper-clad plate are shown in the table I.
Application example 3
100g of the polyphenylene ether resin B obtained in example II, 25g of dicyclopentadiene epoxy resin (NPPN272H, south Asia plastic) and 40g of fused silica were each dissolved in butanone solvent, and then mixed uniformly and adjusted to a suitable viscosity to form a dope.
Soaking 2116 glass cloth in the glue solution, drying the glass cloth to remove butanone to obtain a prepreg, and pressing and curing 8 layers of the prepreg at 180 ℃ for 2 hours to obtain a copper-clad plate with the thickness of 0.9-1.1mm, wherein the properties of the copper-clad plate are shown in the table I.
Application example 4
50g of the polyphenylene ether resin A obtained in example one, 100g of the polyphenylene ether resin B obtained in example two and 40g of fused silica were dissolved in butanone solvent, mixed uniformly and adjusted to a suitable viscosity to form a dope.
Soaking 2116 glass cloth in the glue solution, drying the glass cloth to remove butanone to obtain a prepreg, and pressing and curing 8 layers of the prepreg at 220 ℃ for 3 hours to obtain a copper-clad plate with the thickness of 0.9-1.1mm, wherein the properties of the copper-clad plate are shown in the table I.
Application example 5
100g of the polyphenylene ether resin C obtained in example III, 1g of benzoyl peroxide and 35g of fused silica were dissolved in butanone solvent, and then mixed uniformly and adjusted to a suitable viscosity to form a gel solution.
Soaking 2116 glass cloth in the glue solution, drying the glass cloth to remove butanone to obtain a prepreg, and pressing and curing 8 layers of the prepreg at 200 ℃ for 3 hours to obtain a copper-clad plate with the thickness of 0.9-1.1mm, wherein the properties of the copper-clad plate are shown in the table I.
Application example 6
100g of the polyphenylene ether resin D obtained in example four, 1g of benzoyl peroxide and 35g of fused silica were dissolved in butanone solvent, and then mixed uniformly and adjusted to a suitable viscosity to form a dope.
Soaking 2116 glass cloth in the glue solution, drying the glass cloth to remove butanone to obtain a prepreg, and pressing and curing 8 layers of the prepreg at 200 ℃ for 3 hours to obtain a copper-clad plate with the thickness of 0.9-1.1mm, wherein the properties of the copper-clad plate are shown in the table I.
Application example 7
50g of the polyphenylene ether resin D obtained in example four, 50g of the polyphenylene ether resin C obtained in example three, 1g of benzoyl peroxide and 35g of fused silica were dissolved in a butanone solvent, and then uniformly mixed and adjusted to a suitable viscosity to form a dope.
Soaking 2116 glass cloth in the glue solution, drying the glass cloth to remove butanone to obtain a prepreg, and pressing and curing 8 layers of the prepreg at 200 ℃ for 3 hours to obtain a copper-clad plate with the thickness of 0.9-1.1mm, wherein the properties of the copper-clad plate are shown in the table I.
Application example 8
100g of the polyphenylene ether resin A obtained in example one, 35g of dicyclopentadiene epoxy resin (NPPN272H, southern Asia plastic), 20g of styrene-butadiene copolymer (Ricon 100, Krevili), 10g of MED type bismaleimide (BMI-5100, DAIWA) and 55g of fused silica were each dissolved in a butanone solvent, and then mixed uniformly and adjusted to a suitable viscosity to form a dope.
Soaking 2116 glass cloth in the glue solution, drying the glass cloth to remove butanone to obtain a prepreg, and pressing and curing 8 layers of the prepreg at 210 ℃ for 3 hours to obtain a copper-clad plate with the thickness of 0.9-1.1mm, wherein the properties of the copper-clad plate are shown in the table I.
Application example 9
100g of the polyphenylene ether resin C obtained in example three, 20g of a styrene butadiene copolymer (Ricon 100, Klevili), 10g of a MED type bismaleimide (BMI-5100, DAIWA), and 45g of spherical silica were each dissolved in a butanone solvent, and then mixed uniformly and adjusted to a suitable viscosity to form a dope.
Soaking 2116 glass cloth in the glue solution, drying the glass cloth to remove butanone to obtain a prepreg, and pressing and curing 8 layers of the prepreg at 210 ℃ for 3 hours to obtain a copper-clad plate with the thickness of 0.9-1.1mm, wherein the properties of the copper-clad plate are shown in the table I.
Application example 10
100g of the polyphenylene ether resin C obtained in example III, 20g of a styrene-butadiene copolymer (Ricon 100, Klevili), 10g of MED type bismaleimide (BMI-5100, DAIWA), 10g of triallyl isocyanurate (Yingjiang reagent) and 45g of spherical silica were each dissolved in a butanone solvent, and then mixed uniformly and adjusted to an appropriate viscosity to form a dope.
Soaking 2116 glass cloth in the glue solution, drying the glass cloth to remove butanone to obtain a prepreg, and pressing and curing 8 layers of the prepreg at 210 ℃ for 3 hours to obtain a copper-clad plate with the thickness of 0.9-1.1mm, wherein the properties of the copper-clad plate are shown in the table I.
Application example 11
100g of the polyphenylene ether resin C obtained in example III, 20g of a styrene-butadiene copolymer (Ricon 100, Klevili), 10g of triallyl isocyanurate (Yingjiang reagent) and 45g of spherical silica were each dissolved in a toluene solvent, and then mixed uniformly and adjusted to a suitable viscosity to form a dope.
Soaking 2116-specification glass cloth in the glue solution, drying the glass cloth to remove toluene to obtain a prepreg, and pressing and curing 8 layers of the prepreg at 210 ℃ for 3 hours to obtain the copper-clad plate with the thickness of 0.9-1.1mm, wherein the performance of the copper-clad plate is shown in the table I.
Comparative example 1
100g of a double-terminal-hydroxyl-group polyphenylene ether resin (SA90, SABIC Co., Ltd.), 20g of a dicyclopentadiene epoxy resin (NPPN272H, south Asia plastic), 0.2g of dimethylimidazole (AR, Wengjiang reagent) and 40g of fused silica were dissolved in a butanone solvent, and then mixed uniformly and adjusted to a suitable viscosity to form a glue solution.
Soaking 2116 glass cloth in the glue solution, drying the glass cloth to remove butanone to obtain a prepreg, and pressing and curing 8 layers of the prepreg at 180 ℃ for 2 hours to obtain a copper-clad plate with the thickness of 0.9-1.1mm, wherein the properties of the copper-clad plate are shown in the table I.
Comparative example 2
100g of methacrylate modified polyphenylene ether (SA9000, SABIC company), 1g of benzoyl peroxide and 35g of fused silica are respectively dissolved in butanone solvent, and then are uniformly mixed and adjusted to proper viscosity to form glue solution.
Soaking 2116 glass cloth in the glue solution, drying the glass cloth to remove butanone to obtain a prepreg, and pressing and curing 8 layers of the prepreg at 200 ℃ for 3 hours to obtain a copper-clad plate with the thickness of 0.9-1.1mm, wherein the properties of the copper-clad plate are shown in the table I.
Performance testing
Carrying out performance test on the copper-clad plates of the application examples 1-11 and the comparative examples 1-2, wherein the test items comprise glass transition temperature (Tg), peel strength, thermal expansion coefficient, T288, dielectric constant, dielectric loss factor and flame retardance, and the detection result is shown in the table I;
the detection method of each detection item is as follows:
glass transition temperature (Tg): the DMA test was used and the measurement was carried out according to the DMA test method specified in IPC-TM-6502.4.24.4.
The peel strength was measured in accordance with GB/T4722-92 (copper foil-clad laminate for printed circuits).
The coefficient of thermal expansion CET was measured according to the IPC-TM-6502.4.41 standard.
T288 was tested according to the IPC-TM-6502.4.24.1 standard.
Dielectric constant and dielectric dissipation factor: the test was carried out according to the method of IPC-TM-6502.5.5.9, and the test frequency was 10 GHz.
Flame retardancy: the flame retardancy was measured according to the flammability test method defined in UL 94.
TABLE I Performance test results
As shown in the table I, the copper-clad plate prepared by the application examples 1 to 11 is obviously superior to the copper-clad plate prepared by the comparative example 1 in the glass transition temperature, the peel strength, the thermal expansion coefficient and the dielectric property, the comparative document 2 provides the copper-clad plate with excellent glass transition temperature, thermal expansion coefficient, dielectric property and flame retardance, and the copper-clad plates of the application examples 1 to 11 and the comparative document 2 are not much different in the glass transition temperature, the thermal expansion coefficient, the dielectric property and the flame retardance, so that the copper-clad plate with the same excellent property, which is prepared by adopting a method different from that of the comparative document 2, is provided. Therefore, the organic silicon modified polyphenyl ether resin has excellent comprehensive performance, can be used for preparing high-frequency circuit substrates, and has great application value.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (25)
1. A silicone-modified polyphenylene ether resin, wherein the polyphenylene ether resin has the structure of formula a:
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 are each independently selected from hydrogen, linear or branched C1-C6 alkyl, C6-C12 aryl substituted or unsubstituted by linear or branched C1-C4 alkyl, C1-C6 haloalkyl, aminoalkyl, alkoxy, cyano and vinyl, R13 is selected from linear or branched C1-C8 alkyl, C1-C8 alkoxy or vinyl, R14 is selected from aminoalkyl, anhydride-substituted C1-C8 alkyl, C1-C8 alkoxy or acrylic-substituted C1-C8 alkyl, R15 is selected from C1-C8 alkoxy or linear or branched C2-C8 alkyl;
n is 2 to 200.
2. A process for the production of the polyphenylene ether resin according to claim 1, which comprises reacting a hydroxy-terminated polyphenylene ether with an organosiloxane to obtain the polyphenylene ether resin; wherein the organosiloxane is KBM602, GF20, KBM1003 or KBM 5103;
the hydroxy-terminated polyphenylene ether has the structure of formula B:
in the formula B, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 are all independently selected from hydrogen, linear or branched C1-C6 alkyl, C6-C12 aryl substituted or not by linear or branched C1-C4 alkyl, C1-C6 haloalkyl, aminoalkyl, alkoxy, cyano and vinyl; n is 2 to 200.
3. The method for producing a polyphenylene ether resin according to claim 2, wherein the reaction of the hydroxy-terminated polyphenylene ether with the organosiloxane is carried out in an organic solvent comprising one or more of an alkane, a ketone, an ether, an ester and an amide.
4. The method for preparing a polyphenylene ether resin according to claim 3, wherein said organic solvent comprises one or more of toluene, xylene, trimethylbenzene, cyclohexanone, methyl isobutyl ketone, N-dimethylformamide, tetrahydrofuran, butyl acetate and petroleum ether.
5. The method for producing a polyphenylene ether resin according to claim 2, further comprising adding a catalyst to a reaction system in which the hydroxy-terminated polyphenylene ether is reacted with the organosiloxane.
6. The method for producing a polyphenylene ether resin according to claim 5, wherein said catalyst comprises one or more of an acid catalyst, a base catalyst, a metal compound catalyst and an ester catalyst.
7. The method for producing a polyphenylene ether resin according to claim 5, wherein said catalyst comprises one or more of sulfuric acid, phosphoric acid, hydrochloric acid, oxalic acid, acetic acid, activated clay, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, sodium ethoxide, lithium acetylacetonate, dibutyltin oxide, tetramethyltitanate, tetrabutyltitanate, calcium oxide, aluminum oxide and magnesium oxide.
8. The method for producing a polyphenylene ether resin according to claim 2, wherein after the reaction of the hydroxy-terminated polyphenylene ether with the organosiloxane is completed, the method further comprises removing impurities from the solution after the completion of the reaction to obtain the polyphenylene ether resin.
9. The method for producing a polyphenylene ether resin according to claim 8, wherein the method for removing impurities employs one or more of inert gas purging, distillation under reduced pressure and distillation at high temperature.
10. The method for producing a polyphenylene ether resin according to claim 2, wherein the molar ratio of the hydroxy-terminated polyphenylene ether to the organosiloxane is 1:0.1 to 2.
11. The method for producing a polyphenylene ether resin according to claim 3, wherein the amount of the organic solvent used is not more than 4 times the amount of the bishydroxypolyphenylene ether used in parts by mass.
12. The method for producing a polyphenylene ether resin according to claim 5, wherein the catalyst is used in an amount of not more than 5% by mass based on the amount of the bishydroxypolyphenylene ether.
13. A resin composition comprising the polyphenylene ether resin according to claim 1.
14. The resin composition according to claim 13, wherein the resin composition further comprises an epoxy resin and/or a resin having a double bond.
15. The resin composition of claim 14, wherein the epoxy resin comprises one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, brominated epoxy resin, and phosphorous epoxy resin.
16. The resin composition of claim 15, wherein the resin with double bonds comprises one or more of styrene-butadiene copolymer, polybutadiene and styrene-butadiene-divinylbenzene copolymer.
17. The resin composition of claim 16, wherein each of the styrene-butadiene copolymer, the polybutadiene, and the styrene-butadiene-divinylbenzene copolymer is independently modified with an amino group, a maleic anhydride group, an epoxy group, an acrylate group, a hydroxyl group, or a carboxyl group.
18. The resin composition of claim 13, wherein the resin composition further comprises an inorganic filler.
19. The resin composition of claim 13, wherein the resin composition further comprises a flame retardant.
20. The resin composition of claim 13, wherein the resin composition further comprises a glue solvent.
21. The resin composition of claim 13, wherein the resin composition further comprises a curing catalyst.
22. The resin composition of claim 13, wherein the resin composition further comprises an initiator.
23. A prepreg comprising a reinforcing material, and the resin composition according to claim 13 attached to the reinforcing material after drying by immersion.
24. A laminate comprising a prepreg according to claim 23.
25. A printed circuit board comprising the prepreg according to claim 23.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910638310.9A CN110423342B (en) | 2019-07-15 | 2019-07-15 | Organic silicon modified polyphenyl ether resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910638310.9A CN110423342B (en) | 2019-07-15 | 2019-07-15 | Organic silicon modified polyphenyl ether resin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110423342A CN110423342A (en) | 2019-11-08 |
| CN110423342B true CN110423342B (en) | 2022-03-11 |
Family
ID=68409624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910638310.9A Active CN110423342B (en) | 2019-07-15 | 2019-07-15 | Organic silicon modified polyphenyl ether resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110423342B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112409592A (en) * | 2019-08-21 | 2021-02-26 | 穗晔实业股份有限公司 | Silane modified polyphenyl ether resin and preparation method thereof |
| CN113004676A (en) * | 2021-03-25 | 2021-06-22 | 林州致远电子科技有限公司 | Low-dielectric thermosetting resin composition with low cost |
| CN113185751A (en) * | 2021-04-23 | 2021-07-30 | 艾蒙特成都新材料科技有限公司 | Halogen-free silicon flame-retardant vinyl resin, preparation method thereof and application thereof in copper-clad plate |
| KR20240000511A (en) * | 2021-04-27 | 2024-01-02 | 에스에이치피피 글로벌 테크놀러지스 비.브이. | Bifunctional sizing agent to improve adhesion to substrates |
| CN113214631A (en) * | 2021-05-21 | 2021-08-06 | 林州致远电子科技有限公司 | Low-dielectric-property thermosetting resin composition prepared from silicon-containing polyphenyl ether |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006104450A (en) * | 2004-09-09 | 2006-04-20 | Shin Etsu Chem Co Ltd | Sulfonic acid salt of polyphenylene ether oligomer and method for producing the same |
| CN106916293A (en) * | 2015-12-25 | 2017-07-04 | 广东生益科技股份有限公司 | A kind of organic-silicon-modified polyphenylene oxide resin, Preparation method and use |
| CN108148196A (en) * | 2016-12-02 | 2018-06-12 | 广东生益科技股份有限公司 | A kind of styryl siloxy polyphenylene oxide resin and its preparation method and application |
| CN109988299A (en) * | 2017-12-29 | 2019-07-09 | 广东生益科技股份有限公司 | A kind of organic-silicon-modified polyphenylene oxide resin and its preparation method and application containing epoxy group |
-
2019
- 2019-07-15 CN CN201910638310.9A patent/CN110423342B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006104450A (en) * | 2004-09-09 | 2006-04-20 | Shin Etsu Chem Co Ltd | Sulfonic acid salt of polyphenylene ether oligomer and method for producing the same |
| CN106916293A (en) * | 2015-12-25 | 2017-07-04 | 广东生益科技股份有限公司 | A kind of organic-silicon-modified polyphenylene oxide resin, Preparation method and use |
| CN108148196A (en) * | 2016-12-02 | 2018-06-12 | 广东生益科技股份有限公司 | A kind of styryl siloxy polyphenylene oxide resin and its preparation method and application |
| CN109988299A (en) * | 2017-12-29 | 2019-07-09 | 广东生益科技股份有限公司 | A kind of organic-silicon-modified polyphenylene oxide resin and its preparation method and application containing epoxy group |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110423342A (en) | 2019-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110423342B (en) | Organic silicon modified polyphenyl ether resin and preparation method and application thereof | |
| TWI495684B (en) | A low dielectric resin composition and a copper foil substrate and a printed circuit board to which the copper foil substrate is used | |
| WO2017107589A1 (en) | Silicone-modified polyphenylene ether resin, preparation method therefor, and use thereof | |
| CN108219371B (en) | Epoxy resin composition, prepreg, laminate, and printed wiring board | |
| KR20050023039A (en) | Resin composition and prepreg for laminate and metal-clad laminate | |
| CN108148196B (en) | Styryl siloxy polyphenylene oxide resin and preparation method and application thereof | |
| CN112080102A (en) | Resin composition, prepreg, insulating film, metal-clad laminate, and printed wiring board provided with same | |
| CN109988299B (en) | Epoxy-containing organic silicon modified polyphenyl ether resin and preparation method and application thereof | |
| CN104629341A (en) | Low-dielectric resin composition, semi-solidified rubber sheet using same, copper clad plate, and circuit board | |
| CN110655536A (en) | Phosphorus-containing compound, phosphorus-containing flame retardant, preparation method and product thereof | |
| US10774266B2 (en) | Flame retardant compound, method of making the same, resin composition and article made therefrom | |
| CN113121586A (en) | Modified maleimide compound and preparation method and application thereof | |
| CN115850710B (en) | Modified bismaleimide prepolymer, resin composition and application of resin composition | |
| WO2017107588A1 (en) | Silicone-modified phenol formaldehyde resin, preparation method therefor, and use thereof | |
| CN116239777A (en) | Modified bismaleimide prepolymer, resin composition and application of resin composition | |
| KR20240008879A (en) | Resin composition, prepreg using the same, resin-added film, resin-added metal foil, metal-clad laminate, and wiring board | |
| TWI656129B (en) | Ester-containing phosphazene compound, preparation method and application | |
| CN109971175B (en) | Modified maleimide resin composition, prepreg and laminated board prepared from same | |
| TWI665247B (en) | Thermosetting resin composition and prepreg and metal foil-clad laminate produced by using same | |
| CN108148202B (en) | Styryl poly (phenylene ether) resin and preparation method and application thereof | |
| WO2020248501A1 (en) | Active ester compound, resin composition, and prepreg, insulating film, metal foil coated laminate and printed circuit board having same | |
| CN115819765A (en) | Epoxy compound-modified maleimide prepolymer, resin composition and application of resin composition | |
| WO2017107590A1 (en) | Polyphenolic compound, preparation method therefor, and use thereof | |
| TWI742643B (en) | Resin composition, prepreg sheet and insulating board using the same | |
| CN110804173B (en) | Polyphenylene ether intermediate, polyphenylene ether derivative, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 526200 Mafang Development Zone, Dasha Town, Zhaoqing City, Guangdong Province (No. es1020 of zone 1 in the southwest) Applicant after: Tongyu new material (Guangdong) Co.,Ltd. Address before: 526200 Mafang Development Zone, Dasha Town, Zhaoqing City, Guangdong Province (No. es1020 of zone 1 in the southwest) Applicant before: GUANGDONG TONGYU ADVANCED MATERIALS CO.,LTD. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |