CN111072979A - Modified hydrocarbon resin prepolymer, copper-clad plate and preparation method thereof - Google Patents
Modified hydrocarbon resin prepolymer, copper-clad plate and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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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
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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Abstract
The invention discloses a modified hydrocarbon resin prepolymer, a copper-clad plate and a preparation method thereof, wherein the modified hydrocarbon resin prepolymer is prepared by mixing and reacting 50-450 parts of hydrocarbon resin, 50 parts by mass of a mixture containing double-bond epoxy resin/maleimide resin, 1-5 parts by mass of an initiator A and 180-280 parts by mass of a solvent A through a microchannel reactor and removing part of the solvent; the modified hydrocarbon resin copper-clad plate is prepared from the following modified hydrocarbon resin prepolymers in percentage by mass: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator B: accelerator A: reinforcement = 90: 10-30: 40-100: 0.01-1: 0.01-1: 70-200 of the composition and a copper foil are thermally cured to prepare a glass fiber copper-clad plate; the modified hydrocarbon resin copper-clad plate prepared by the invention has the characteristics of low dielectric constant, low dielectric loss, low water absorption, high glass transition temperature and high peel strength.
Description
Technical Field
The invention belongs to modified hydrocarbon resin, a copper-clad plate (laminated plate) and preparation thereof, and relates to a modified hydrocarbon resin prepolymer, a copper-clad plate and a preparation method thereof. The modified hydrocarbon resin prepolymer is particularly suitable for manufacturing high-frequency and high-speed copper-clad plates with 5G communication requirements.
Background
Due to the requirements of 5G communication data transmission rate and high reliability, the technical difficulties which need to be overcome in the aspects of dielectric constant, dielectric loss factor, heat resistance and the like are caused when the laminated board and the copper-clad plate are used.
The hydrocarbon resin has excellent dielectric properties (volume resistivity of 10) due to the small polarity of C-H in the molecular chain (the electronegativity of C and H is 2.5 and 2.1 respectively)17～18Omega.m; a dielectric constant (1MHz) of 2.4 to 2.8; tan delta of 0.0002 to 0.0006), which has been gaining more and more attention in recent years. However, the hydrocarbon resin has problems of insufficient rigidity, low strength, poor heat resistance, low glass transition temperature (Tg), low peel strength, and the like in the cured product due to its flexibility and nonpolar carbon chain structure, and thus its use is limited. It is well studied and improved by those skilled in the art, for example: CN104845366A, CN106243430A, CN106221126A, CN109810467A, CN109867912A, CN106589748A, CN108676209A and the like, but the aim of improving the heat resistance is achieved by means of forming a composition by a hydrocarbon resin and a heat-resistant resin and then forming a polymer by crosslinking an initiator initiating system. Because the reaction belongs to free radical polymerization, the polymerization speed is high, the polymers are easy to implode, and the molecular weight distribution of the polymers is not goodUniformity and a large number of internally dense inhomogeneities in the product are highly susceptible to inevitable damage such as stress cracking and crazing during daily use.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a modified hydrocarbon resin prepolymer, a copper-clad plate and a preparation method thereof. The invention adopts hydrocarbon resin, modified resin, initiator and the like to carry out modification reaction in a pipeline reactor (namely a microchannel reactor) to synthesize the modified hydrocarbon resin prepolymer with uniform molecular weight distribution, high heat resistance, low dielectric constant and low dielectric loss, the modified hydrocarbon resin prepolymer provides high-viscosity framework support, is very beneficial to stable crosslinking during the later-stage plate pressing, and further provides a copper-clad plate with good performance and a preparation method thereof.
The invention relates to a modified hydrocarbon resin prepolymer which is characterized by being prepared by mixing and reacting 50-450 parts of hydrocarbon resin, 50 parts by mass of a mixture of double-bond-containing epoxy resin and maleimide resin, 1-5 parts by mass of an initiator A and 180-280 parts by mass of a composition ① of a solvent A through a microchannel reactor and removing part of the solvent.
The invention comprises the following steps: the number average molecular weight of the modified hydrocarbon resin prepolymer ranges from 8000 to 30000, the solid content ranges from 68 to 72%, and the vinyl content ranges from 20% to 80%.
Another aspect of the invention is: a preparation method of modified hydrocarbon resin prepolymer is characterized by comprising the following steps:
firstly, adding 50-450 parts by mass of hydrocarbon resin, 50 parts by mass of a mixture of double-bond-containing epoxy resin/maleimide resin and 150-230 parts by mass of a solvent A ⑴ into a mixing tank ①, heating to 30-60 ℃, stirring and dissolving to obtain a (transparent) liquid material A for later use;
secondly, adding 1-5 parts by mass of initiator A and 30-50 parts by mass of solvent A ⑵ into a mixing tank ②, heating to 30-60 ℃, stirring for dissolving (transparent), and preparing a liquid material B for later use;
thirdly, connecting a liquid material A and a liquid material B into a microchannel reactor with the temperature set to be 80-150 ℃ by two feeding pipes, controlling (setting) the feeding speed of the liquid material A to be 20-100 ml/min and the feeding speed of the liquid material B to be 2-10 ml/min, mixing and reacting the liquid material A and the liquid material B in a microchannel reactor channel, cooling the liquid material A and the liquid material B to 10-50 ℃ in a cooling pipe (of the microchannel reactor), discharging, putting the liquid material A into a vacuum tank with the temperature of 10-60 ℃ and pumping out part of solvent A to ensure that the solid content of hydrocarbon resin is 68-72 percent, thus obtaining the modified hydrocarbon resin prepolymer;
the hydrocarbon resin is one or a mixture of more than two of styrene-butadiene resin, polybutadiene resin, polyisobutylene resin, polypentadiene resin, styrene-butadiene copolymer, styrene-isobutylene copolymer, styrene-divinylbenzene copolymer, polystyrene, 2-methyl polystyrene, 3-methyl polystyrene, 4-methyl polystyrene, 2, 4-diisopropyl polystyrene, 2, 4-dimethyl polystyrene, ethylene-propylene-diene copolymer and cycloolefin copolymer; the hydrocarbon resin production enterprises include Korea brochure, Changhong high-tech, Dushan petrochemical, Klebsiella, Caoda, Balin petrochemical, etc.;
in the mixture of the double-bond-containing epoxy resin/maleimide resin, the mass ratio of the double-bond-containing epoxy resin to the maleimide resin is as follows: maleimide resin ═ 1: 1-9; the enterprises providing the double-bond epoxy resin comprise Kunshan south Asia, Shandong Laiwu Runda and the like; the production enterprises of the maleimide resin have eastern material science and technology, new Qingdao Baichen materials and the like;
the initiator a is a peroxide, azo, redox type initiator, such as: dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile or a mixture of more than two of the above components;
the solvent A is one or a mixture of more than two of acetone, butanone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide and methyl isobutyl ketone.
In another aspect of the present invention, the chemical structure of the maleimide resin is represented by formula ① below:
①
in the formula: n is 0 to 10, R1is-CH2-、-SO2、-O-、-CO-、-S2-、-(CH2)2-、-(CH2)4-、 -(CH2)6-、-(CH2)8-、-(CH2)10-，-(CH2)12-，
R2Is H, -CH3、-C2H5-、-C3H7-、-COOH、-NO2、-CH＝CH2、-CH2-CH＝CH2-C ≡ CH, tert-butyl, phenyl, methacryloyl; r3、R4Is H, -CH3；
The chemical structure of the double bond-containing epoxy resin is represented by the following formulas ② and ③:
②
in the formula: n is 0 to 7, R5Is H, -CH3,R6is-CH2-、-C2H4-、-O-CH2-；
③
In the formula: n is 0 to 7, R7is-CH2-、-C(CH3)2-、-SO2、-O-、-CO-。
The definition of the amount of solids is: 1g of the sample (i.e., the obtained modified hydrocarbon resin) was baked in an oven at 160 ℃ for 1 hour, and the mass of the non-volatile matter was calculated based on the mass of the non-volatile matter, and the mass of the added solvent was calculated to adjust the amount of the solid.
The vinyl content is defined as: in 1g of the sample (i.e., the obtained modified hydrocarbon resin), the vinyl group was contained in a percentage by mass of the total mass number.
The microchannel reactor may be any one of a corning microchannel reactor, a Shandong Haimai microchannel reactor, a Suzhou Wensha micro-reactor, a Shanghai micro-reactor, a Mijing technology microchannel reactor, a Chengzhi microchannel reactor, and a Frouk microchannel reactor.
Another aspect of the invention is: a modified hydrocarbon resin copper-clad plate is characterized in that: the modified hydrocarbon resin copper-clad plate is prepared from the following modified hydrocarbon resin prepolymers in percentage by mass: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator B: accelerator A: reinforcing material 90: 10-30: 40-100: 0.01-1: 0.01-1: 70-200 of the composition and a copper foil are thermally cured to prepare a glass fiber copper-clad plate;
the modified hydrocarbon resin prepolymer, i.e., the modified hydrocarbon resin prepolymer (prepared) above;
the initiator B is a peroxide, azo, redox type initiator, such as: dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile or a mixture of more than two of the above components;
the accelerator A is one or a mixture of more than two of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-methyl-4-phenylimidazole.
The modified hydrocarbon resin copper-clad plate has excellent comprehensive performance and the technical performance is as follows: the dielectric constant is less than or equal to 3.60; the dielectric loss is less than or equal to 0.004; the water absorption is less than or equal to 0.15 percent; the peel strength is more than or equal to 0.7N/m; the glass transition temperature Tg is more than or equal to 240 ℃; it has the characteristics of low dielectric constant, low dielectric loss, low water absorption, high glass transition temperature and high peel strength.
Another aspect of the invention is: a preparation method of a modified hydrocarbon resin copper-clad plate is characterized by comprising the following steps:
a. preparing a modified hydrocarbon resin prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator C: accelerator B: solvent B ═ 90: 10-30: 40-100: 0.01-1: 0.01-1: 73-86 of taking the modified hydrocarbon resin prepolymer, the high-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin, the inorganic filler, the initiator C, the accelerator B and the solvent B, uniformly mixing to obtain a combined feed liquid, putting the reinforcing material into the combined feed liquid (fully) for dipping, taking out, and baking at the temperature of 120-185 ℃ for 1-10 min to obtain a modified hydrocarbon resin prepreg;
b. preparing a modified hydrocarbon resin copper-clad plate:
cutting and superposing the modified hydrocarbon resin prepreg and the metal copper foil according to the length, width and thickness requirements, then placing the prepreg and the metal copper foil into a hot press, keeping the heating rate at 1-3 ℃/min, heating to 80-150 ℃, pressing for 1-3 hours under the pressure of 0.2-1 MPa and the temperature of 80-150 ℃, then continuing heating, keeping the heating rate at 1-3 ℃/min, heating to 180-250 ℃, and pressing for 1-6 hours under the pressure of 2-7 MPa and the temperature of 180-250 ℃ to obtain the modified hydrocarbon resin copper-clad plate;
the modified hydrocarbon resin prepolymer, i.e., the modified hydrocarbon resin prepolymer (prepared) above;
the inorganic filler is one or a mixture of more than two of montmorillonite, calcium carbonate, magnesium hydroxide, zinc borate, talc, aluminum hydroxide, kaolin, barium sulfate, silica micropowder, mica powder, hollow glass beads and fumed silica;
the initiator C is a peroxide, azo, redox type initiator, such as: dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile or a mixture of more than two of the above components;
the accelerator B is one or a mixture of more than two of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-methyl-4-phenylimidazole;
the solvent B is one or a mixture of more than two of acetone, butanone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide and methyl isobutyl ketone;
the copper foil has no limitation on the thickness.
The high-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin is one or a mixture of more than two of the compounds with the following chemical structural formulas of ④ - ⑥:
④
⑤
⑥
the reinforcing material is any one of organic synthetic fiber, natural fiber, organic fabric and inorganic fabric; for example: glass fibers, cotton fibers, and the like.
The prepared modified hydrocarbon resin copper-clad plate has excellent comprehensive performance, and the technical performance is as follows: the dielectric constant is less than or equal to 3.60; the dielectric loss is less than or equal to 0.004; the water absorption is less than or equal to 0.15 percent; the peel strength is more than or equal to 0.7N/m; the glass transition temperature Tg is more than or equal to 240 ℃; the high-strength low-dielectric-constant high-glass-transition-temperature-resistant high-peel-strength high-dielectric-constant high-glass-transition-temperature-resistant high-strength high-glass-transition-temperature-resistant high-peel-strength high-dielectric-constant high-strength.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) according to the invention, the hydrocarbon resin is modified with double bond-containing epoxy and maleimide to form a prepolymer, and a high temperature-resistant imide ring and an epoxy group with good bonding force with a substrate are introduced into the system, so that the heat resistance and peel strength of the system can be effectively improved;
(2) according to the invention, the hydrocarbon resin and the modified resin are subjected to prepolymerization reaction to form the modified hydrocarbon resin prepolymer, so that the problems of high polymerization speed, strong heat release, easy implosion, uneven polymer molecular weight distribution (the molecular weight distribution coefficient is 1.2-1.3), easy cracking and silver streaks during the use of a plate can be effectively avoided when the hydrocarbon resin is directly pressed into a plate without prepolymerization and the reaction belongs to free radical polymerization;
(3) the invention adopts the microchannel reactor (which is a device sold in the market) to carry out modification prepolymerization reaction on hydrocarbon resin for the first time, and the microchannel reactor has the characteristics of extremely narrow reaction residence time, high-efficiency quality and heat transfer, accurate control on reaction conditions, high-efficiency and safe production and the like, so that the implosion and heat accumulation caused by high free radical polymerization speed can be effectively avoided, the molecular weight of the product is controllable, the distribution is uniform (the molecular weight distribution coefficient is 1.0-1.07), and the byproducts are less;
(4) in the modified hydrocarbon resin copper-clad plate, the fluorenyl-containing benzoxazine resin (namely the high-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin) is added into the formula, so that the epoxy in the modified hydrocarbon resin prepolymer is subjected to ring-opening curing, and the high heat resistance and the excellent dielectric property of the high-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin further reduce the dielectric constant and the dielectric loss of a system and further reduce the water absorption;
(5) the copper-clad plate prepared by the composition for the copper-clad plate (namely a combined feed liquid obtained by uniformly mixing a modified hydrocarbon resin prepolymer, a high-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin, an inorganic filler, an initiator C, an accelerator B and a solvent B) has the technical properties that: the dielectric constant is less than or equal to 3.60; the dielectric loss is less than or equal to 0.004; the water absorption is less than or equal to 0.15 percent; the peel strength is more than or equal to 0.7N/m; the glass transition temperature Tg is more than or equal to 240 ℃; the resin has the characteristics of low dielectric constant, low dielectric loss, low water absorption, high glass transition temperature and high peel strength, has excellent comprehensive performance, and can be used as resin for a high-frequency and high-speed copper-clad plate.
(6) The product of the invention has simple preparation process, easy operation, good product performance and strong practicability.
Detailed Description
The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.
First part preparation of modified Hydrocarbon resin prepolymer
The basic process comprises the following steps of 1) adding 50-450 parts by mass of hydrocarbon resin, 50 parts by mass of a resin mixture containing double-bond epoxy/maleimide and 150-230 parts by mass of a solvent A ⑴ into a mixing tank, heating to 30-60 ℃, and stirring for dissolving to obtain a transparent liquid material A for later use;
2) adding 1-5 parts by mass of an initiator I and 30-50 parts by mass of a solvent A ⑵ into a reactor II, heating to 30-60 ℃, stirring for dissolving, and obtaining a liquid material B for later use;
3) connecting a liquid material A and a liquid material B into a microchannel reactor with the temperature set to be 80-150 ℃ by two feeding pipes, wherein the inner diameter of each feeding pipe is 3mm, the feeding speed of the liquid material A is set (and controlled) to be 20-100 ml/min, the feeding speed of the liquid material B is 2-10 ml/min, the liquid material A and the liquid material B enter a discharging pipe with a cooling medium after mixed reaction in a microchannel reactor channel, immediately cooling to be 10-50 ℃ for discharging, putting the discharging pipe into a vacuum tank with the temperature of 10-60 ℃ and extracting part of solvent A to ensure that the solid content of hydrocarbon resin is 70 +/-2 percent, thus obtaining the modified hydrocarbon resin prepolymer;
table 1: raw material dosage (unit: kg) and process parameter table for preparing modified hydrocarbon resin
Note: in the table, hydrocarbon resin i: ricon 181; a hydrocarbon resin II: SODA B-1000; hydrocarbon resin III: ricon142
Formula of second part modified hydrocarbon resin copper-clad plate combined feed liquid
Preparing modified hydrocarbon resin prepolymer in the mass ratio: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator C: accelerator B: solvent B ═ 90: 10-30: 40-100: 0.01-1: 0.01-1: 73-86 parts of modified hydrocarbon resin copper-clad plate combined material liquid, and uniformly mixing.
Table 2: dosage of raw materials of formula of modified hydrocarbon resin composition feed liquid (unit: kg)
The preparation method of the modified hydrocarbon resin copper-clad plate combined feed liquid of embodiment 2-1-2-8 comprises the following steps: the modified hydrocarbon resin, the high-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin, the inorganic filler, the initiator, the accelerator and the solvent are stirred and mixed uniformly, and the solid content is 62-75%.
Preparing a prepreg: placing the reinforcing material into the combined material liquid (fully) for soaking, taking out, and baking at 120-185 ℃ for 1-10 min to obtain a modified hydrocarbon resin prepreg;
preparing a modified hydrocarbon resin copper-clad plate: cutting and superposing the modified hydrocarbon resin prepreg and the metal copper foil according to the length, width and thickness requirements, then placing the prepreg and the metal copper foil into a hot press, keeping the heating rate at 1-3 ℃/min, pressing the prepreg and the metal copper foil for 1-3 hours at the pressure of 0.2-1 MPa and the temperature of 80-150 ℃ after reaching the temperature, then continuing heating, keeping the heating rate at 1-3 ℃/min, and pressing the prepreg and the metal copper foil for 1-6 hours at the pressure of 2-7 MPa and the temperature of 180-250 ℃ after reaching the temperature to obtain the modified hydrocarbon resin prepreg and the metal copper foil;
the comparison of partial technical performances of the modified hydrocarbon resin copper-clad plate prepared by the invention and the comparative plate is shown in the following table 3:
table 3: the modified hydrocarbon resin copper-clad plate is compared with a comparative plate in part of technical performances:
comparative examples 1 and 2 are test data of an outsourced hydrocarbon resin copper clad laminate.
The technical performance test methods in table 3 are as follows:
(1) dielectric constant
The dielectric constant at 1GHz was measured by the plate method according to IPC-TM-650, 2.5.5.9.
(2) Dielectric loss tangent
The dielectric loss tangent at 1GHz was measured by the plate method according to IPC-TM-650, 2.5.5.9.
(3) Peel strength
The peel strength of the metal cap was tested according to the experimental conditions of "thermal stress" in the method specified by 2.4.8 in IPC-TM-650.
(4) Water absorption rate
The measurement was carried out according to the method defined in IPC-TM-650, 2.6.2.1.
(5) Glass transition temperature (Tg)
According to differential scanning calorimetry, the measurement was carried out according to the DSC method defined by 2.4.25 in IPC-TM-650.
As can be seen from table 3, the sheet obtained by applying the examples of the present invention has excellent heat resistance, lower dielectric constant and dielectric loss tangent, higher peel strength and lower water absorption. The composition can be used in the fields of laminated boards, integrated circuit packaging, high-frequency high-speed copper-clad plates, high-density internet and the like, and has wide application prospect.
Example 3:
a modified hydrocarbon resin prepolymer is prepared by mixing and reacting 50 parts by mass of a hydrocarbon resin, 50 parts by mass of a double bond-containing epoxy resin/maleimide resin mixture, 1 part by mass of an initiator A and 180 parts by mass of a solvent A in a microchannel reactor, and removing part of the solvent.
Example 4:
a modified hydrocarbon resin prepolymer is prepared by mixing and reacting 450 parts by mass of a hydrocarbon resin, 50 parts by mass of a double bond-containing epoxy resin/maleimide resin mixture, 5 parts by mass of an initiator A and 280 parts by mass of a solvent A in a microchannel reactor, and removing part of the solvent.
Example 5:
a modified hydrocarbon resin prepolymer is prepared by mixing and reacting 250 hydrocarbon resin, 50 parts by mass of a double bond-containing epoxy resin/maleimide resin mixture, 3 parts by mass of an initiator A and 230 parts by mass of a solvent A in a microchannel reactor to remove a part of the solvent, wherein the initiator A is a compound ①.
Example 6:
a preparation method of a modified hydrocarbon resin prepolymer comprises the following steps:
firstly, adding 50 parts by mass of hydrocarbon resin, 50 parts by mass of a mixture of double-bond-containing epoxy resin/maleimide resin and 150 parts by mass of a solvent A ⑴ into a mixing tank ①, heating to 30 ℃, and stirring for dissolving to obtain a (transparent) liquid material A for later use;
secondly, adding 1 part by mass of initiator A and 30 parts by mass of solvent A ⑵ into a mixing tank ②, heating to 30 ℃, stirring for dissolving (transparent), and preparing a liquid material B for later use;
and thirdly, connecting a liquid material A and a liquid material B into a microchannel reactor with the temperature set to be 80 ℃ by two feeding pipes, controlling (setting) the feeding speed of the liquid material A to be 20ml/min and the feeding speed of the liquid material B to be 2ml/min, mixing and reacting the liquid material A and the liquid material B in a channel of the microchannel reactor, cooling the mixture to 10 ℃ in a cooling pipe (the cooling pipe of the microchannel reactor, and then cooling the mixture), discharging the mixture, putting the cooled mixture into a vacuum tank with the temperature of 10 ℃ and pumping out part of the solvent A to ensure that the solid content of the hydrocarbon resin is 68 percent, thus obtaining the modified hydrocarbon resin prepolymer.
Example 7:
a preparation method of a modified hydrocarbon resin prepolymer comprises the following steps:
firstly, adding 450 parts by mass of hydrocarbon resin, 50 parts by mass of a mixture of double-bond-containing epoxy resin/maleimide resin and 230 parts by mass of a solvent A ⑴ into a mixing tank ①, heating to 60 ℃, and stirring for dissolving to obtain a (transparent) liquid material A for later use;
secondly, adding 5 parts by mass of initiator A and 50 parts by mass of solvent A ⑵ into a mixing tank ②, heating to 60 ℃, stirring for dissolving (transparent), and preparing a liquid material B for later use;
and thirdly, connecting a liquid material A and a liquid material B into a microchannel reactor with the temperature of 150 ℃ by using two feeding pipes, wherein the inner diameters of the feeding pipes are both 3mm, controlling (setting) the feeding speed of the liquid material A to be 100ml/min and the feeding speed of the liquid material B to be 10ml/min, mixing and reacting the liquid material A and the liquid material B in a channel of the microchannel reactor, cooling the mixture to 50 ℃ in a cooling pipe, discharging the mixture, putting the mixture into a vacuum tank with the temperature of 60 ℃, pumping out part of the solvent A, and enabling the solid content of the hydrocarbon resin to be 72 percent, thereby preparing the modified hydrocarbon resin prepolymer.
Example 8:
a preparation method of a modified hydrocarbon resin prepolymer comprises the following steps:
firstly, adding 250 parts by mass of hydrocarbon resin, 50 parts by mass of a mixture of double-bond epoxy resin/maleimide resin and 190 parts by mass of a solvent A ⑴ into a mixing tank ①, heating to 45 ℃, stirring and dissolving to obtain a (transparent) liquid material A for later use;
secondly, adding 3 parts by mass of initiator A and 40 parts by mass of solvent A ⑵ into a mixing tank ②, heating to 45 ℃, stirring for dissolving (transparent), and preparing a liquid material B for later use;
and thirdly, connecting a liquid material A and a liquid material B into a microchannel reactor with the temperature set to be 120 ℃ by using two feeding pipes, wherein the inner diameters of the feeding pipes are both 3mm, controlling (setting) the feeding speed of the liquid material A to be 60ml/min and the feeding speed of the liquid material B to be 6ml/min, mixing and reacting the liquid material A and the liquid material B in a channel of the microchannel reactor, cooling the mixture to be 30 ℃ in a cooling pipe, discharging the mixture, putting the mixture into a vacuum tank with the temperature of 35 ℃, pumping out part of the solvent A, and enabling the solid content of the hydrocarbon resin to be 70%, so as to obtain the modified hydrocarbon resin prepolymer.
In the above embodiments 6 to 8:
the hydrocarbon resin is one or a mixture of more than two of styrene-butadiene resin, polybutadiene resin, polyisobutylene resin, polypentadiene resin, styrene-butadiene copolymer, styrene-isobutylene copolymer, styrene-divinylbenzene copolymer, polystyrene, 2-methyl polystyrene, 3-methyl polystyrene, 4-methyl polystyrene, 2, 4-diisopropyl polystyrene, 2, 4-dimethyl polystyrene, ethylene-propylene-diene copolymer and cycloolefin copolymer; the hydrocarbon resin production enterprises include Korea brochure, Changhong high-tech, Dushan petrochemical, Klebsiella, Caoda, Balin petrochemical, etc.;
in the mixture of the double-bond-containing epoxy resin/maleimide resin, the mass ratio of the double-bond-containing epoxy resin to the maleimide resin is as follows: maleimide resin ═ 1: 1-9; the enterprises providing the double-bond epoxy resin comprise Kunshan south Asia, Shandong Laiwu Runda and the like; the production enterprises of the maleimide resin have eastern material science and technology, new Qingdao Baichen materials and the like;
the initiator a is a peroxide, azo, redox type initiator, such as: dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile or a mixture of more than two of the above components;
the solvent A is one or a mixture of more than two of acetone, butanone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide and methyl isobutyl ketone.
In the above examples 6 to 8, the chemical structure of the maleimide resin is represented by the following formula ①:
①
in the formula: n is 0 to 10, R1is-CH2-、-SO2、-O-、-CO-、-S2-、-(CH2)2-、-(CH2)4-、 -(CH2)6-、-(CH2)8-、-(CH2)10-，-(CH2)12-，
R2Is H, -CH3、-C2H5-、-C3H7-、-COOH、-NO2、-CH＝CH2、-CH2-CH＝CH2-C ≡ CH, tert-butyl, phenyl, methacryloyl; r3、R4Is H, -CH3；
The chemical structure of the double bond-containing epoxy resin is represented by the following formulas ② and ③:
②
in the formula: n is 0 to 7, R5Is H, -CH3,R6is-CH2-、-C2H4-、-O-CH2-；
③
In the formula: n is 0 to 7, R7is-CH2-、-C(CH3)2-、-SO2、-O-、-CO-。
The definition of the amount of solids is: 1g of the sample (i.e., the obtained modified hydrocarbon resin) was baked in an oven at 160 ℃ for 1 hour, and the mass of the non-volatile matter was calculated based on the mass of the non-volatile matter, and the mass of the added solvent was calculated to adjust the amount of the solid.
The vinyl content is defined as: in 1g of the sample (i.e., the obtained modified hydrocarbon resin), the vinyl group was contained in a percentage by mass of the total mass number.
The microchannel reactor may be any one of a corning microchannel reactor, a Shandong Haimai microchannel reactor, a Suzhou Wensha micro-reactor, a Shanghai micro-reactor, a Mijing technology microchannel reactor, a Chengzhi microchannel reactor, and a Frouk microchannel reactor.
Example 9:
a modified hydrocarbon resin copper-clad plate is prepared by the following components in percentage by mass: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator B: accelerator A: reinforcing material 90: 10: 40: 0.01: 0.01: 70 and copper foil are thermally cured to prepare the glass fiber copper-clad plate.
Example 10:
a modified hydrocarbon resin copper-clad plate is prepared by the following components in percentage by mass: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator B: accelerator A: reinforcing material 90: 30: 100: 1: 1: 200 and copper foil are thermally cured to prepare the glass fiber copper-clad plate.
Example 11:
a modified hydrocarbon resin copper-clad plate is prepared by the following components in percentage by mass: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator B: accelerator A: reinforcing material 90: 20: 70: 0.05: 0.05: 80 and copper foil are thermally cured to prepare the glass fiber copper-clad plate.
In the above embodiments 9 to 11:
the modified hydrocarbon resin prepolymer, i.e., the modified hydrocarbon resin prepolymer (prepared) above;
the initiator B is a peroxide, azo, redox type initiator, such as: dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile or a mixture of more than two of the above components;
the accelerator A is one or a mixture of more than two of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-methyl-4-phenylimidazole.
Example 12:
a preparation method of a modified hydrocarbon resin copper-clad plate comprises the following steps:
a. preparing a modified hydrocarbon resin prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator C: accelerator B: solvent B ═ 90: 10: 40: 0.01: 0.01: 73, uniformly mixing the modified hydrocarbon resin prepolymer, the high-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin, the inorganic filler, the initiator C, the accelerator B and the solvent B to obtain a combined feed liquid, putting the reinforcing material into the combined feed liquid (fully) for soaking, taking out, and baking at 120 ℃ for 10min to obtain a modified hydrocarbon resin prepreg;
b. preparing a modified hydrocarbon resin copper-clad plate:
cutting and superposing the modified hydrocarbon resin prepreg and the metal copper foil according to the length, width and thickness requirements, then placing the prepreg and the metal copper foil into a hot press, keeping the heating rate at 1 ℃/min, heating to 80 ℃, pressing for 3 hours under the pressure of 0.2MPa and the temperature of 80 ℃, then continuing heating, keeping the heating rate at 1 ℃/min, heating to 180 ℃, and pressing for 6 hours under the pressure of 2MPa and the temperature of 180 ℃ to obtain the modified hydrocarbon resin copper-clad plate.
Example 13:
a preparation method of a modified hydrocarbon resin copper-clad plate comprises the following steps:
a. preparing a modified hydrocarbon resin prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator C: accelerator B: solvent B ═ 90: 30: 100: 1: 1: 86, uniformly mixing the modified hydrocarbon resin prepolymer, the high-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin, the inorganic filler, the initiator C, the accelerator B and the solvent B to obtain a combined feed liquid, putting the reinforcing material into the combined feed liquid (fully) for soaking, taking out, and baking at 185 ℃ for 1min to obtain a modified hydrocarbon resin prepreg;
b. preparing a modified hydrocarbon resin copper-clad plate:
cutting and superposing the modified hydrocarbon resin prepreg and the metal copper foil according to the length, width and thickness requirements, then placing the prepreg and the metal copper foil into a hot press, keeping the heating rate at 3 ℃/min, heating to 150 ℃, pressing for 1 hour under the pressure of 1MPa and the temperature of 150 ℃, then continuing heating, keeping the heating rate at 3 ℃/min, heating to 250 ℃, and pressing for 1 hour under the pressure of 7MPa and the temperature of 250 ℃ to obtain the modified hydrocarbon resin copper-clad plate.
Example 14:
a preparation method of a modified hydrocarbon resin copper-clad plate comprises the following steps:
a. preparing a modified hydrocarbon resin prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator C: accelerator B: solvent B ═ 90: 20: 70: 0.06: 0.06: 80, uniformly mixing the modified hydrocarbon resin prepolymer, the high-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin, the inorganic filler, the initiator C, the accelerator B and the solvent B to obtain a combined feed liquid, putting the reinforcing material into the combined feed liquid (fully) for soaking, taking out, and baking at the temperature of 155 ℃ for 6min to obtain a modified hydrocarbon resin prepreg;
b. preparing a modified hydrocarbon resin copper-clad plate:
cutting and superposing the modified hydrocarbon resin prepreg and the metal copper foil according to the length, width and thickness requirements, then placing the prepreg and the metal copper foil into a hot press, keeping the heating rate at 2 ℃/min, heating to 120 ℃, pressing for 2 hours at the pressure of 0.6MPa and the temperature of 120 ℃, then continuing heating, keeping the heating rate at 2 ℃/min, heating to 215 ℃, and pressing for 3.5 hours at the pressure of 4.5MPa and the temperature of 215 ℃ to obtain the modified hydrocarbon resin copper-clad plate.
Example 15:
a preparation method of a modified hydrocarbon resin copper-clad plate comprises the following steps:
a. preparing a modified hydrocarbon resin prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator C: accelerator B: solvent B ═ 90: 16: 55: 0.03: 0.03: 76, uniformly mixing the modified hydrocarbon resin prepolymer, the high-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin, the inorganic filler, the initiator C, the accelerator B and the solvent B to obtain a combined feed liquid, putting the reinforcing material into the combined feed liquid (fully) for soaking, taking out, and baking at the temperature of 135 ℃ for 8min to obtain a modified hydrocarbon resin prepreg;
b. preparing a modified hydrocarbon resin copper-clad plate:
cutting and superposing the modified hydrocarbon resin prepreg and the metal copper foil according to the length, width and thickness requirements, then placing the prepreg and the metal copper foil into a hot press, keeping the heating rate at 2 ℃/min, heating to 90 ℃, pressing for 3 hours at the pressure of 0.4MPa and the temperature of 90 ℃, then continuing heating, keeping the heating rate at 2 ℃/min, heating to 200 ℃, and pressing for 5 hours at the pressure of 3MPa and the temperature of 200 ℃ to obtain the modified hydrocarbon resin copper-clad plate.
Example 16:
a preparation method of a modified hydrocarbon resin copper-clad plate comprises the following steps:
a. preparing a modified hydrocarbon resin prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator C: accelerator B: solvent B ═ 90: 25: 85: 0.08: 0.08: 83 taking the modified hydrocarbon resin prepolymer, the high-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin, the inorganic filler, the initiator C, the accelerator B and the solvent B, uniformly mixing to obtain a combined feed liquid, putting the reinforcing material into the combined feed liquid (fully) for soaking, taking out, and baking at 175 ℃ for 4min to obtain a modified hydrocarbon resin prepreg;
b. preparing a modified hydrocarbon resin copper-clad plate:
cutting and superposing the modified hydrocarbon resin prepreg and the metal copper foil according to the length, width and thickness requirements, then placing the prepreg and the metal copper foil into a hot press, keeping the heating rate at 2 ℃/min, heating to 140 ℃, pressing for 2 hours at the pressure of 0.8MPa and the temperature of 140 ℃, then continuing heating, keeping the heating rate at 2 ℃/min, heating to 240 ℃, and pressing for 2.5 hours at the pressure of 6MPa and the temperature of 240 ℃ to obtain the modified hydrocarbon resin copper-clad plate.
In the above embodiments 12 to 16:
the modified hydrocarbon resin prepolymer, i.e., the modified hydrocarbon resin prepolymer (prepared) above;
the inorganic filler is one or a mixture of more than two of montmorillonite, calcium carbonate, magnesium hydroxide, zinc borate, talc, aluminum hydroxide, kaolin, barium sulfate, silica micropowder, mica powder, hollow glass beads and fumed silica;
the initiator C is a peroxide, azo, redox type initiator, such as: dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile or a mixture of more than two of the above components;
the accelerator B is one or a mixture of more than two of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-methyl-4-phenylimidazole;
the solvent B is one or a mixture of more than two of acetone, butanone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide and methyl isobutyl ketone;
the copper foil has no limitation on the thickness.
In embodiments 12 to 16, the high heat resistance, high toughness, and low dielectric fluorenyl benzoxazine resin is one or a mixture of two or more of the following compounds having chemical structural formulas of ④ to ⑥:
④
⑤
⑥
in the above embodiments 12 to 16: the reinforcing material is any one of organic synthetic fiber, natural fiber, organic fabric and inorganic fabric; for example: glass fibers, cotton fibers, and the like.
In the above embodiments 9 to 16: the modified hydrocarbon resin copper-clad plate (prepared) has excellent comprehensive performance, and the technical performance is as follows: the dielectric constant is less than or equal to 3.60; the dielectric loss is less than or equal to 0.004; the water absorption is less than or equal to 0.15 percent; the peel strength is more than or equal to 0.7N/m; the glass transition temperature Tg is more than or equal to 240 ℃; the resin has the characteristics of low dielectric constant, low dielectric loss, low water absorption, high glass transition temperature and high peel strength, and can be used as resin for a high-frequency and high-speed copper-clad plate.
In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the proportions used, not specifically noted, are mass (weight) proportions; the parts by weight may each be grams or kilograms.
In the above embodiment: the process parameters (temperature, time, pressure, etc.) and the amounts of the components in each step are within the range, and any point can be applicable.
The present invention and the technical contents not specifically described in the above examples are the same as those of the prior art, and the raw materials are all commercially available products.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.
Claims (9)
1. The modified hydrocarbon resin prepolymer is characterized by being prepared by mixing and reacting 50-450 parts of hydrocarbon resin, 50 parts by mass of a double-bond epoxy resin/maleimide resin mixture, 1-5 parts by mass of an initiator A and 180-280 parts by mass of a composition ① of a solvent A through a microchannel reactor and removing part of the solvent.
2. The modified hydrocarbon resin prepolymer as claimed in claim 1, wherein: the number average molecular weight of the modified hydrocarbon resin prepolymer ranges from 8000 to 30000, the solid content ranges from 68 to 72%, and the vinyl content ranges from 20% to 80%.
3. A preparation method of modified hydrocarbon resin prepolymer is characterized by comprising the following steps:
firstly, adding 50-450 parts by mass of hydrocarbon resin, 50 parts by mass of a mixture of double-bond-containing epoxy resin/maleimide resin and 150-230 parts by mass of a solvent A ⑴ into a mixing tank ①, heating to 30-60 ℃, stirring and dissolving to obtain a liquid material A for later use;
secondly, adding 1-5 parts by mass of initiator A and 30-50 parts by mass of solvent A ⑵ into a mixing tank ②, heating to 30-60 ℃, stirring and dissolving to obtain a liquid material B for later use;
thirdly, connecting a liquid material A and a liquid material B into a microchannel reactor with the temperature set to be 80-150 ℃ by two feeding pipes, controlling the inner diameters of the feeding pipes to be 3mm, controlling the feeding speed of the liquid material A to be 20-100 ml/min and the feeding speed of the liquid material B to be 2-10 ml/min, mixing and reacting the liquid material A and the liquid material B in a microchannel reactor channel, cooling the mixture to 10-50 ℃ in a cooling pipe, discharging, putting the mixture into a vacuum tank with the temperature of 10-60 ℃ and pumping out part of the solvent A to ensure that the solid content of the hydrocarbon resin is 68-72 percent, thus obtaining the modified hydrocarbon resin prepolymer;
the hydrocarbon resin is one or a mixture of more than two of styrene-butadiene resin, polybutadiene resin, polyisobutylene resin, polypentadiene resin, styrene-butadiene copolymer, styrene-isobutylene copolymer, styrene-divinylbenzene copolymer, polystyrene, 2-methyl polystyrene, 3-methyl polystyrene, 4-methyl polystyrene, 2, 4-diisopropyl polystyrene, 2, 4-dimethyl polystyrene, ethylene-propylene-diene copolymer and cycloolefin copolymer;
in the mixture of the double-bond-containing epoxy resin/maleimide resin, the mass ratio of the double-bond-containing epoxy resin to the maleimide resin is as follows: maleimide resin ═ 1: 1-9;
the initiator A is one or a mixture of more than two of dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile;
the solvent A is one or a mixture of more than two of acetone, butanone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide and methyl isobutyl ketone.
4. The process for preparing a modified hydrocarbon resin prepolymer as claimed in claim 3, wherein the maleimide resin has a chemical structure represented by the following formula ①:
①
in the formula: n is 0 to 10, R1is-CH2-、-SO2、-O-、-CO-、-S2-、-(CH2)2-、-(CH2)4-、-(CH2)6-、-(CH2)8-、-(CH2)10-，-(CH2)12-，
R2Is H, -CH3、-C2H5-、-C3H7-、-COOH、-NO2、-CH＝CH2、-CH2-CH＝CH2-C ≡ CH, tert-butyl, phenyl, methacryloyl; r3、R4Is H, -CH3；
The chemical structure of the double bond-containing epoxy resin is represented by the following formulas ② and ③:
②
in the formula: n is 0 to 7, R5Is H, -CH3,R6is-CH2-、-C2H4-、-O-CH2-；
③
In the formula: n is 0 to 7, R7is-CH2-、-C(CH3)2-、-SO2、-O-、-CO-。
5. A modified hydrocarbon resin copper-clad plate is characterized in that: the modified hydrocarbon resin copper-clad plate is prepared from the following modified hydrocarbon resin prepolymers in percentage by mass: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator B: accelerator A: reinforcing material 90: 10-30: 40-100: 0.01-1: 0.01-1: 70-200 of the composition and a copper foil are thermally cured to prepare a glass fiber copper-clad plate;
the initiator B is one or a mixture of more than two of dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile;
the accelerator A is one or a mixture of more than two of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-methyl-4-phenylimidazole.
6. A preparation method of a modified hydrocarbon resin copper-clad plate is characterized by comprising the following steps:
a. preparing a modified hydrocarbon resin prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: high heat resistance, high toughness and low dielectric fluorenyl benzoxazine resin: inorganic filler: an initiator C: accelerator B: solvent B ═ 90: 10-30: 40-100: 0.01-1: 0.01-1: 73-86 of taking a modified hydrocarbon resin prepolymer, a high-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin, an inorganic filler, an initiator C, an accelerator B and a solvent B, uniformly mixing to obtain a combined feed liquid, putting a reinforcing material into the combined feed liquid, soaking, taking out, and baking at the temperature of 120-185 ℃ for 1-10 min to obtain a modified hydrocarbon resin prepreg;
b. preparing a modified hydrocarbon resin copper-clad plate:
cutting and superposing the modified hydrocarbon resin prepreg and the metal copper foil according to the length, width and thickness requirements, then placing the prepreg and the metal copper foil into a hot press, keeping the heating rate at 1-3 ℃/min, heating to 80-150 ℃, pressing for 1-3 hours under the pressure of 0.2-1 MPa and the temperature of 80-150 ℃, then continuing heating, keeping the heating rate at 1-3 ℃/min, heating to 180-250 ℃, and pressing for 1-6 hours under the pressure of 2-7 MPa and the temperature of 180-250 ℃ to obtain the modified hydrocarbon resin copper-clad plate;
the inorganic filler is one or a mixture of more than two of montmorillonite, calcium carbonate, magnesium hydroxide, zinc borate, talc, aluminum hydroxide, kaolin, barium sulfate, silica micropowder, mica powder, hollow glass beads and fumed silica;
the initiator C is one or a mixture of more than two of dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile;
the accelerator B is one or a mixture of more than two of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-methyl-4-phenylimidazole;
the solvent B is one or a mixture of more than two of acetone, butanone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide and methyl isobutyl ketone.
7. The preparation method of the modified hydrocarbon resin copper-clad plate according to claim 6, wherein the high heat resistance and high toughness low dielectric fluorenyl benzoxazine resin is one or a mixture of more than two of the compounds with the following chemical structural formulas of ④ - ⑥:
④
⑤
⑥
8. the preparation method of the modified hydrocarbon resin copper-clad plate according to claim 6 or 7, which is characterized by comprising the following steps: the reinforcing material is any one of organic synthetic fiber, natural fiber, organic fabric, inorganic fabric.
9. The preparation method of the modified hydrocarbon resin copper-clad plate according to claim 6 or 7, which is characterized by comprising the following steps: the technical performance of the prepared modified hydrocarbon resin copper-clad plate is as follows: the dielectric constant is less than or equal to 3.60; the dielectric loss is less than or equal to 0.004; the water absorption is less than or equal to 0.15 percent; the peel strength is more than or equal to 0.7N/m; the glass transition temperature Tg is more than or equal to 240 ℃.
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