CN113462143B - Polyphenylene ether resin composition, and prepreg and laminate prepared using the same - Google Patents
Polyphenylene ether resin composition, and prepreg and laminate prepared using the same Download PDFInfo
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- CN113462143B CN113462143B CN202110669453.3A CN202110669453A CN113462143B CN 113462143 B CN113462143 B CN 113462143B CN 202110669453 A CN202110669453 A CN 202110669453A CN 113462143 B CN113462143 B CN 113462143B
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention discloses a polyphenyl ether resin composition, and a prepreg and a laminated board prepared by using the polyphenyl ether resin composition, which comprise the following components: 100 parts by weight of allyl modified polyphenyl ether resin; 5-20 parts by weight of trifunctional allyl resin; 1-10 parts by weight of a vinyl epoxy resin cross-linking agent; 10-50 parts by weight of polyfunctional epoxy resin; 10-60 parts by weight of allyl modified attapulgite clay; 1.5-6 parts by weight of an initiator composition. According to the invention, after the polyphenyl ether is modified by allyl, the vinyl epoxy resin cross-linking agent is used for cross-linking and curing with the epoxy resin, so that the block network-shaped high polymer is formed, the glass transition temperature, toughness, heat resistance, solvent resistance and other performances of the polyphenyl ether resin can be improved, and the prepared laminated board has low dielectric constant and dielectric loss, and is very suitable for being used as a circuit substrate of high-frequency high-speed electronic equipment.
Description
Technical Field
The invention relates to the field of polyphenyl ether resin, in particular to a polyphenyl ether resin composition, and a prepreg and a laminated board prepared by using the polyphenyl ether resin composition.
Background
With the development of high performance and networking of electronic devices such as information communication and computers, signal transmission tends to be high-speed and high-frequency, so that the dielectric performance requirements on circuit substrate materials are higher and higher. The FR-4 board using epoxy resin as matrix for the current PCB has difficulty in meeting the requirements of high frequency and high speed. The polyphenyl ether resin has very low dielectric constant and dielectric loss, high glass transition temperature and low water absorption, and is an ideal substrate of a high-frequency copper-clad plate.
However, polyphenylene oxide is a thermoplastic material, and when the polyphenylene oxide is applied to a copper-clad plate substrate, the polyphenylene oxide has the problems of poor aromatic and halogen solvent resistance, insufficient heat resistance and the like. Therefore, it is necessary to thermoset-modify polyphenylene ether to improve its heat resistance, solvent resistance, and the like.
Disclosure of Invention
The invention aims to: aiming at the problems in the prior art, the invention provides a polyphenyl ether resin composition, a prepreg and a laminated board prepared by using the polyphenyl ether resin composition, and uses a vinyl epoxy resin cross-linking agent to crosslink and solidify polyphenyl ether, trifunctional allyl resin, allyl modified attapulgite clay powder and epoxy resin through one-step free radical polymerization and cationic polymerization, so as to form an attapulgite clay modified polyphenyl ether, epoxy resin and polyacrylate block polymer which has a three-dimensional network structure, thereby improving the glass transition temperature, toughness, heat resistance, solvent resistance and flame retardance of the polyphenyl ether resin.
The technical scheme is as follows: the invention provides a polyphenyl ether resin composition, which comprises the following components: 100 parts by weight of allyl modified polyphenyl ether resin; 5-20 parts by weight of trifunctional allyl resin; 1-10 parts by weight of vinyl epoxy resin cross-linking agent; 10-50 parts by weight of polyfunctional epoxy resin; 10-60 parts by weight of allyl modified attapulgite clay; 1.5-6 parts by weight of an initiator composition.
Preferably, the allyl modified polyphenylene ether resin is prepared by the following method: dissolving allyl functionalized isocyanate and hydroxyl-terminated polyphenyl ether resin in an organic solvent to form a homogeneous solution, stirring at room temperature for 30-120 min, pouring into a large amount of methanol to precipitate after the reaction is finished, and vacuum drying to obtain the allyl modified polyphenyl ether resin.
Preferably, the molar ratio of the hydroxyl-terminated polyphenylene ether resin to the allyl-functionalized isocyanate is 1: 2-4.
Preferably, the allyl functionalized isocyanate is any one of the following: isocyanatoethyl methacrylate, isocyanatoethyl acrylate, 3-isocyanatopropylene; the organic solvent is any one of the following: chloroform, toluene, xylene, tetrahydrofuran; the number average molecular weight of the hydroxyl-terminated polyphenyl ether resin is 2500-5000.
Preferably, the trifunctional allyl resin is any one of the following: triallylamine, triallylphosphine, triallylphosphate, triallylborate; the vinyl epoxy resin cross-linking agent is any one of the following: 4-vinyl-1-cyclohexene-1, 2-epoxide, 3, 4-epoxide-1-butene; the polyfunctional epoxy resin is any one of the following: 4,4' -isopropylidenediphenol diglycidyl ether, resorcinol diglycidyl ether, 1, 7-octadiene diglycidyl compound, tris (4-hydroxyphenyl) methane triglycidyl ether, 1, 3-bis (3-glycidylether oxypropyl) tetramethyl disiloxane.
Preferably, the allyl modified attapulgite clay is prepared by the following method: and adding allyl functionalized isocyanate into 2 weight percent of attapulgite clay/N, N Dimethylformamide (DMF) dispersion liquid, stirring for 120 min at room temperature, washing with DMF after the reaction is finished, and drying in vacuum to obtain the allyl modified attapulgite clay powder.
Preferably, the initiator is a combination of a free radical initiator and a cationic initiator.
Preferably, the free radical initiator is any one of the following: dicumyl peroxide, di-tert-butyldiisopropylbenzene peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 2, 4-dichlorobenzoyl peroxide; the cationic initiator is 2-methyl-alpha- [2- [ [ propylsulfonyl ] imine ] -3 (2H) -thiophene methylene-benzyl cyanide.
The invention also provides a prepreg prepared from the polyphenyl ether resin composition, which is prepared by dissolving the polyphenyl ether resin composition in a solvent to prepare a glue solution, and then dipping the glass fiber cloth in the glue solution, and then heating and drying the glass fiber cloth to obtain the prepreg.
The invention also provides a laminated board prepared from the prepreg, wherein one side or two sides of one prepreg are covered with copper foil, or at least two prepregs are overlapped, and then the copper foil is covered on one side or two sides of the prepreg, and the laminated board is obtained through hot press molding.
The beneficial effects are that: 1. according to the invention, vinyl epoxy resin is used as a cross-linking agent, and is cross-linked and cured with trifunctional allyl resin, allyl modified attapulgite clay and epoxy resin after allyl modification of polyphenyl ether, so that a three-dimensional network structure is formed, and the glass transition temperature, toughness, heat resistance, solvent resistance and other properties of the polyphenyl ether resin can be improved, so that the prepared laminated board has low dielectric constant and dielectric loss;
2. according to the invention, phosphorus and nitrogen-containing trifunctional allyl monomers and allyl modified attapulgite clay are adopted, and are grafted into the polyphenyl ether resin through in-situ reaction, so that the flame retardant property of the polyphenyl ether resin and prepregs and laminated boards prepared from the polyphenyl ether resin can be improved;
3. the invention innovatively obtains the modified polyphenyl ether polymer by adopting the combination of the free radical initiator and the cationic initiator and carrying out one-step in-situ polymerization on allyl and epoxy functional groups, thereby avoiding the use of amine curing agents (curing agents most commonly used for epoxy resin), reducing the water absorption rate of the polymer and improving the dielectric property of the polymer;
4. compared with the prior art, the preparation process of the allyl modified polyphenyl ether provided by the invention only needs to uniformly mix the solutions, and the solution is stirred at room temperature for reaction, so that the preparation process is simple, the operation is convenient, the equipment requirement is low, and the preparation process is suitable for industrial production.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Embodiment 1:
100 parts by weight of a hydroxyl-terminated polyphenylene ether resin and 40 parts by weight of isocyanoethyl methacrylate were dissolved in 1500 parts by weight of chloroform, stirred at room temperature for 60 minutes, poured into a large amount of methanol to precipitate after the reaction was completed, and dried in vacuo to obtain an allyl-modified polyphenylene ether resin.
0.5. 0.5 mL allyl functionalized isocyanate is added into 100 mL parts by weight of an attapulgite clay/N, N Dimethylformamide (DMF) dispersion, stirred at room temperature for 120 min, and after the reaction is finished, the mixture is washed with DMF and dried in vacuum to obtain allyl modified attapulgite clay.
The above 100 parts by weight of an allyl-modified polyphenylene ether resin, 5 parts by weight of triallyl phosphate, 10 parts by weight of an allyl-modified attapulgite clay, 1 part by weight of 3, 4-epoxy-1-butene, 10 parts by weight of a 1, 7-octadiene diepoxide compound, 1 part by weight of di-t-butylperoxydiisopropylbenzene, 0.5 part by weight of 2-methyl-alpha- [2- [ [ propionyl ] imine ] -3 (2H) -thiophenemethylene-benzyl cyanide were dissolved in 200 parts by weight of chloroform to obtain a resin composition, namely a dope.
E-glass fiber cloth (model 7628) is soaked in the glue solution for 1-2 min, and then heated and dried at 60 ℃ for 3-5 min, so that the prepreg is obtained.
Copper foil with the thickness of 35 mu m is coated on each of the two sides of the prepreg, and the prepreg is hot-pressed for 30 min at the temperature of 180 ℃ and the pressure of 5 MPa, so that a double-sided copper-clad laminated board is obtained.
Embodiment 2:
100 parts by weight of a hydroxyl-terminated polyphenylene ether resin and 30 parts by weight of isocyanate ethyl acrylate were dissolved in 1000 parts by weight of tetrahydrofuran, stirred at room temperature for 30 minutes, poured into a large amount of methanol to precipitate after the reaction was completed, and vacuum-dried to obtain an allyl-modified polyphenylene ether resin.
The preparation method of the allyl modified attapulgite clay is exactly the same as that of the embodiment 1, and is not described here.
The above 100 parts by weight of an allyl-modified polyphenylene ether resin, 10 parts by weight of triallylphosphine, 20 parts by weight of an allyl-modified attapulgite clay, 3 parts by weight of 3, 4-epoxy-1-butene, 15 parts by weight of 4,4' -isopropylidenediphenol diglycidyl ether, 2 parts by weight of dicumyl peroxide, 1 part by weight of 2-methyl-alpha- [2- [ [ propylsulfonyl ] imine ] -3 (2H) -thiophene methylene-benzyl cyanide were dissolved in 150 parts by weight of tetrahydrofuran to obtain a resin composition, namely a dope.
E-glass fiber cloth (model 7628) is soaked in the glue solution for 1-2 min, and then heated and dried at 80 ℃ for 3-5 min, so that the prepreg is obtained.
After 5 prepregs are stacked, copper foils with the thickness of 35 mu m are coated on the two sides of the prepreg, and the prepreg is hot-pressed for 60 minutes at the temperature of 170 ℃ and the pressure of 10 MPa, so that a double-sided copper-coated laminated board is obtained.
Embodiment 3:
100 parts by weight of a hydroxyl-terminated polyphenylene ether resin and 20 parts by weight of 3-isocyanatopropylene were dissolved in 600 parts by weight of toluene, stirred at room temperature for 40 minutes, poured into a large amount of methanol to precipitate after the reaction was completed, and vacuum-dried to obtain an allyl-modified polyphenylene ether resin.
The preparation method of the allyl modified attapulgite clay is exactly the same as that of the embodiment 1, and is not described here.
The above-mentioned 100 parts by weight of an allyl-modified polyphenylene ether resin, 20 parts by weight of triallylamine, 30 parts by weight of an allyl-modified attapulgite clay, 5 parts by weight of 4-vinyl-1-cyclohexene-1, 2-epoxy, 25 parts by weight of resorcinol diglycidyl ether, 2 parts by weight of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 1 part by weight of 2-methyl- α - [2- [ [ propane sulfonyl ] imine ] -3 (2H) -thiophene methylene-phenylacetonitrile were dissolved in 100 parts by weight of toluene to obtain a resin composition, namely a dope.
E-glass fiber cloth (model 7628) is soaked in the glue solution for 1-2 min, and then heated and dried at 115 ℃ for 5-10 min, so that the prepreg is obtained.
Copper foil with a thickness of 35 μm is coated on each of the two sides of the prepreg, and the prepreg is hot-pressed for 90 min at a temperature of 175 ℃ and a pressure of 7 MPa, thereby obtaining a double-sided copper-clad laminate.
Embodiment 4:
the preparation method of the allyl modified polyphenylene ether resin is exactly the same as that of embodiment 1, and a detailed description thereof will be omitted.
The preparation method of the allyl modified attapulgite clay is exactly the same as that of the embodiment 1, and is not described here.
The above-mentioned 100 parts by weight of an allyl-modified polyphenylene ether resin, 20 parts by weight of triallylamine, 60 parts by weight of an allyl-modified attapulgite clay, 10 parts by weight of 4-vinyl-1-cyclohexene-1, 2-epoxy, 50 parts by weight of tris (4-hydroxyphenyl) methane triglycidyl ether, 3 parts by weight of 2, 4-dichlorobenzoyl peroxide, 3 parts by weight of 2-methyl-alpha- [2- [ [ propionyl ] imine ] -3 (2H) -thiophene methylene-phenylacetonitrile were dissolved in 100 parts by weight of toluene to obtain a resin composition, namely a dope.
E-glass fiber cloth (model 7628) is soaked in the glue solution for 1-2 min, and then heated and dried at 115 ℃ for 5-10 min, so that the prepreg is obtained.
Copper foil with the thickness of 35 mu m is coated on each of the two sides of the prepreg, and the prepreg is hot-pressed for 90 min at the temperature of 180 ℃ and the pressure of 7 MPa, so that a double-sided copper-clad laminated board is obtained.
The physical properties of the above examples are shown in Table 1, in which the glass transition temperature Tg and the thermal decomposition temperature Td were measured by DSC and TG, respectively, and the dielectric properties were measured according to IPC-TM-650.2.5.5.9 using the flat panel method, and the flame retardant rating was measured according to the UL94 standard.
Table 1 physical property data for examples 1 to 4
| Physical Properties | Example 1 | Example 2 | Example 3 | Example 4 |
| Tg（℃） | 184 | 180 | 169 | 161 |
| Td（℃） | 421 | 408 | 392 | 375 |
| Dk（1GHz） | 3.46 | 3.63 | 3.84 | 3.98 |
| Df（1 GHz） | 0.0032 | 0.0035 | 0.0043 | 0.0048 |
| Flame retardant rating | V1 | V1 | V0 | V0 |
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (7)
1. A polyphenyl ether resin composition is characterized by comprising the following components: 100 parts by weight of allyl modified polyphenyl ether resin; 5-20 parts by weight of trifunctional allyl resin; 1-10 parts by weight of vinyl epoxy resin cross-linking agent; 10-50 parts by weight of polyfunctional epoxy resin; 10-60 parts by weight of allyl modified attapulgite clay; 1.5-6 parts by weight of an initiator composition;
wherein the vinyl epoxy resin cross-linking agent is any one of the following: 4-vinyl-1-cyclohexene-1, 2-epoxide, 3, 4-epoxide-1-butene;
the initiator is a combination of a free radical initiator and a cationic initiator; the free radical initiator is any one of the following: dicumyl peroxide, di-tert-butyldiisopropylbenzene peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 2, 4-dichlorobenzoyl peroxide; the cationic initiator is 2-methyl-alpha- [2- [ [ propylsulfonyl ] imine ] -3 (2H) -thiophene methylene-benzyl cyanide;
the allyl modified attapulgite clay is prepared by the following method:
and adding allyl functionalized isocyanate into 2 weight percent of attapulgite clay/N, N Dimethylformamide (DMF) dispersion liquid, stirring for 120 min at room temperature, washing with DMF after the reaction is finished, and drying in vacuum to obtain the allyl modified attapulgite clay powder.
2. The polyphenylene ether resin composition according to claim 1, wherein the allyl modified polyphenylene ether resin is prepared by the process of:
dissolving allyl functionalized isocyanate and hydroxyl-terminated polyphenyl ether resin in an organic solvent to form a homogeneous solution, stirring at room temperature for 30-120 min, pouring into a large amount of methanol to precipitate after the reaction is finished, and vacuum drying to obtain the allyl modified polyphenyl ether resin.
3. The polyphenylene ether resin composition according to claim 2, wherein the molar ratio of the hydroxyl terminated polyphenylene ether resin to the allyl functionalized isocyanate is 1: 2-4.
4. The polyphenylene ether resin composition according to claim 2, wherein the allyl functionalized isocyanate is any one of the following: isocyanatoethyl methacrylate, isocyanatoethyl acrylate, 3-isocyanatopropylene;
the organic solvent is any one of the following: chloroform, toluene, xylene, tetrahydrofuran;
the number average molecular weight of the hydroxyl-terminated polyphenyl ether resin is 2500-5000.
5. The polyphenylene ether resin composition according to claim 1, wherein the trifunctional allyl resin is any one of the following:
triallylamine, triallylphosphine, triallylphosphate, triallylborate;
the polyfunctional epoxy resin is any one of the following: 4,4' -isopropylidenediphenol diglycidyl ether, resorcinol diglycidyl ether, 1, 7-octadiene diglycidyl compound, tris (4-hydroxyphenyl) methane triglycidyl ether, 1, 3-bis (3-glycidylether oxypropyl) tetramethyl disiloxane.
6. A prepreg prepared from the polyphenylene ether resin composition according to any one of claims 1 to 5, wherein the polyphenylene ether resin composition is dissolved in a solvent to prepare a glue solution, and then a glass fiber cloth is impregnated with the glue solution and then heated and dried to obtain the prepreg.
7. A laminate made from the prepreg of claim 6, wherein one side or both sides of one of the prepregs is clad with copper foil, or at least two of the prepregs are stacked and then clad with copper foil on one side or both sides thereof, and the laminate is obtained by hot press molding.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467967A (en) * | 2013-09-16 | 2013-12-25 | 广东生益科技股份有限公司 | Thermosetting resin composition and use thereof |
| CN109715734A (en) * | 2016-10-17 | 2019-05-03 | 松下知识产权经营株式会社 | Resin combination, the manufacturing method of resin combination, prepreg, the film of resin, the metal foil of resin, metal-clad laminate and wiring plate |
| CN110177820A (en) * | 2017-01-10 | 2019-08-27 | 住友精化株式会社 | Composition epoxy resin |
| CN110387065A (en) * | 2019-07-29 | 2019-10-29 | 江苏点金石凹土矿业有限公司 | A kind of preparation method of superfine high-purity sodium base Concave-convex clay rod flame retardant |
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| TWI678390B (en) * | 2017-01-20 | 2019-12-01 | 台燿科技股份有限公司 | Resin composition, and prepreg, metal-clad laminate, and printed circuit board using the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467967A (en) * | 2013-09-16 | 2013-12-25 | 广东生益科技股份有限公司 | Thermosetting resin composition and use thereof |
| CN109715734A (en) * | 2016-10-17 | 2019-05-03 | 松下知识产权经营株式会社 | Resin combination, the manufacturing method of resin combination, prepreg, the film of resin, the metal foil of resin, metal-clad laminate and wiring plate |
| CN110177820A (en) * | 2017-01-10 | 2019-08-27 | 住友精化株式会社 | Composition epoxy resin |
| CN110387065A (en) * | 2019-07-29 | 2019-10-29 | 江苏点金石凹土矿业有限公司 | A kind of preparation method of superfine high-purity sodium base Concave-convex clay rod flame retardant |
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