CN111072980B - Modified hydrocarbon resin prepolymer, modified hydrocarbon-DCPD epoxy composite material copper-clad plate and preparation method - Google Patents

Modified hydrocarbon resin prepolymer, modified hydrocarbon-DCPD epoxy composite material copper-clad plate and preparation method Download PDF

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CN111072980B
CN111072980B CN201911388844.7A CN201911388844A CN111072980B CN 111072980 B CN111072980 B CN 111072980B CN 201911388844 A CN201911388844 A CN 201911388844A CN 111072980 B CN111072980 B CN 111072980B
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支肖琼
黄杰
唐安斌
李建学
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Sichuan Dongcai Technology Group Co Ltd
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    • 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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    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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Abstract

The invention discloses a modified hydrocarbon resin prepolymer, a modified hydrocarbon-DCPD epoxy composite copper-clad plate and a preparation method thereof, wherein the modified hydrocarbon resin prepolymer is prepared by mixing and reacting 50-200 parts by mass of hydrocarbon resin, 50 parts by mass of a resin mixture containing double bond benzoxazine resin/modified polyphenyl ether resin, 1-5 parts by mass of an initiator A and 110-280 parts by mass of a solvent A through a microchannel reactor and removing part of the solvent. The modified carbon-hydrogen-DCPD epoxy composite material copper-clad laminate is prepared from the following modified carbon-hydrogen resin prepolymers in percentage by mass: DCPD epoxy 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 copper foil are subjected to thermosetting to obtain the copper foil; has the characteristics of low dielectric constant, low dielectric loss, low water absorption, high glass transition temperature and high peel strength.

Description

Modified hydrocarbon resin prepolymer, modified hydrocarbon-DCPD epoxy composite material copper-clad plate and preparation method
Technical Field
The invention belongs to the field of synthesis of modified hydrocarbon resin and preparation of composite material plates, and relates to a modified hydrocarbon resin prepolymer, a modified hydrocarbon-DCPD epoxy composite material 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 is 0.0002-0.0006), and people pay more and more attention in recent years; on the other hand, the hydrocarbon resin does not contain a flame retardant group and a group with good bonding force with a substrate basically in the structure, so that the cured product has poor flame retardancy and low peel strength, and the cured product has the problems of insufficient rigidity, poor heat resistance, low glass transition temperature (Tg) and the like due to the flexible and nonpolar carbon chain structure, so that the use of the hydrocarbon resin is limited. It has now been subjected to numerous studies and improvements by those skilled in the art, such as: CN104845366A, CN106243430A, CN106221126A, CN109810467A, CN109867912A, CN106589748A, CN108676209A and the like, but the aims of improving the heat resistance and increasing the peeling strength are achieved by means of forming a composition by a hydrocarbon resin and a resin with high heat resistance and high adhesive force and then forming a polymer by crosslinking through an initiator initiating system. As the reaction belongs to free radical polymerization, the polymerization speed is high, the polymer is easy to implode, the molecular weight distribution of the polymer is not uniform, and a large number of internal dense uneven states in a product are easy to cause inevitable damage such as stress cracking and crazing in daily use.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a modified hydrocarbon resin prepolymer, a modified hydrocarbon-DCPD epoxy composite copper-clad plate and a preparation method thereof. According to the invention, hydrocarbon resin, modified resin, an initiator and the like are adopted to carry out modification reaction in a pipeline reactor (namely a microchannel reactor), so as to synthesize a high-heat-resistance, low-dielectric constant and low-dielectric-loss modified hydrocarbon resin prepolymer with uniform molecular weight distribution, wherein the modified hydrocarbon resin prepolymer provides a high-viscosity skeleton support, thereby being very beneficial to stable crosslinking during later-stage plate pressing, and then is cured with DCPD epoxy to form matrix resin of a copper-clad plate so as to improve the comprehensive performance of the copper-clad plate; further provides a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate with good performance and a preparation method thereof.
The content of the invention is as follows: a modified hydrocarbon resin prepolymer, characterized by: the modified hydrocarbon resin prepolymer is prepared by mixing and reacting 50-200 parts by mass of hydrocarbon resin, 50 parts by mass of a resin mixture containing double-bond benzoxazine resin/modified polyphenylene ether resin, 1-5 parts by mass of an initiator A and 110-280 parts by mass 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 prepared modified hydrocarbon resin prepolymer is 8000-30000, the solid content is 68-72%, and the vinyl content is 20-80%.
Another aspect of the invention is: a preparation method of modified hydrocarbon resin prepolymer is characterized by comprising the following steps:
firstly, adding 50-200 parts by mass of hydrocarbon resin, 50 parts by mass of a resin mixture containing double-bond benzoxazine resin/modified polyphenyl ether resin and 80-230 parts by mass of a solvent A (1) into a mixing tank, heating to 30-60 ℃, stirring and dissolving to prepare 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 (2) into a mixing tank II, 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, setting the inner diameter of each feeding pipe to be 3mm, setting (namely controlling) the feeding speed of the liquid material A to be 20-100 ml/min, 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 be 10-50 ℃ in a cooling pipe (of the microchannel reactor), discharging the mixture, putting the mixture into a vacuum tank with the temperature of 10-60 ℃, pumping out part of solvent A, and enabling the solid content to be 68-72%, 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.;
the resin mixture of the double-bond-containing benzoxazine resin/modified polyphenyl ether resin comprises the following components in percentage by mass: modified polyphenylene ether resin ═ 1: 1-9; the production enterprises of benzoxazine resin containing double bonds have eastern wood science and technology; the manufacturers of modified polyphenylene ether resins include sabik, asahi chemical compounds, 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 invention: the double bond-containing benzoxazine resin is one or a mixture of more than two of compounds with chemical structural formulas shown as the following formulas:
①
Figure BDA0002344380320000031
in formula (I): r1Is composed of
Figure BDA0002344380320000032
And k is 0 or 1, R2Is H, C1～C12Alkyl, vinyl, allyl, phenyl, amino, nitro, naphthylOr cyclohexyl; r3Is H, -CH3；
②
Figure BDA0002344380320000033
Formula (II): r4Is vinyl, allyl or a structure of formula (III) R5is-CH2-、-C(CH3)2-、-SO2、-O-、-CO-；
③
Figure BDA0002344380320000041
Formula (III): r6H, allyl, nitro, alkynyl and the like;
④
Figure BDA0002344380320000042
in the formula (IV): r7is-CH2-、-SO2，R8is-CH2-、-C2H4-、-O-CH2-；
In another aspect of the invention: the chemical structural formula of the modified polyphenyl ether resin is represented by the formula (v):
⑤
Figure BDA0002344380320000043
in the formula: n is 5 to 20, R9/R10The molecular structure of the compound is a molecular structure of which the terminal contains an active group of allyl, vinyl or styryl.
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 (which is a commercially available device) may be any one of a corning microchannel reactor, a Shandong Haimai microchannel reactor, a Suzhou Venturi micro-reactor, a Shanghai micro-reactor, a Mitsubishi microchannel reactor, a Mitsubishi technology microchannel reactor, a Chengxian microchannel reactor, and a Frouk microchannel reactor.
Another aspect of the invention is: a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate is characterized in that: the modified carbon-hydrogen-DCPD epoxy composite material copper-clad laminate is prepared from the following modified carbon-hydrogen resin prepolymers in percentage by mass: DCPD epoxy 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 structure of the DCPD epoxy resin (namely dicyclopentadiene phenol type epoxy resin) is as follows:
⑥
Figure BDA0002344380320000051
in the formula, n is an integer of 1-10;
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 copper foil has no limitation on the thickness.
The modified carbon-hydrogen-DCPD epoxy composite copper-clad plate has excellent comprehensive performance and the technical performance is as follows: the dielectric constant is less than or equal to 3.40; dielectric loss is less than or equal to 0.003; the water absorption is less than or equal to 0.15 percent; the peel strength is more than or equal to 0.8N/m; the glass transition temperature Tg is more than or equal to 230 ℃; flame retardance: UL-V0 level; the copper clad laminate 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 a high-frequency high-speed copper clad laminate.
Another aspect of the invention is: a preparation method of a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate is characterized by comprising the following steps:
a. preparing a modified carbon hydrogen-DCPD epoxy composite prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: DCPD epoxy 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 DCPD epoxy resin, the inorganic filler, the initiator C, the accelerator B and the solvent B, uniformly mixing to obtain modified hydrocarbon-DCPD epoxy composite copper-clad plate combined feed liquid, putting the reinforcing material into the modified hydrocarbon-DCPD epoxy composite copper-clad plate 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-DCPD epoxy composite prepreg;
b. preparing a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate:
cutting and superposing the modified carbon-hydrogen-DCPD epoxy composite 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 for 1-3 hours at the pressure of 0.2-1 MPa and the temperature of 80-150 ℃ after reaching the temperature (namely the temperature of 80-150 ℃), then continuing heating, keeping the heating rate at 1-3 ℃/min, pressing for 1-6 hours at the pressure of 2-7 MPa and the temperature of 180-250 ℃ after reaching the temperature (namely the temperature of 180-250 ℃), and thus obtaining the modified carbon-hydrogen-DCPD epoxy composite copper clad plate;
the modified hydrocarbon resin prepolymer, i.e., the modified hydrocarbon resin prepolymer (prepared) above;
the chemical structure of the DCPD epoxy resin (namely dicyclopentadiene phenol type epoxy resin, production enterprises have Shandong Laiwu Runda, Country chemical industry, Guangzhou Taiji new material and the like) is represented by the following formula (i):
⑥
Figure BDA0002344380320000061
in the formula, n is an integer of 1-10;
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 unlimited thickness;
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 carbon-hydrogen-DCPD epoxy composite copper-clad plate has excellent comprehensive performance and the technical performance is as follows: the dielectric constant is less than or equal to 3.40; dielectric loss is less than or equal to 0.003; the water absorption is less than or equal to 0.15 percent; the peel strength is more than or equal to 0.8N/m; the glass transition temperature Tg is more than or equal to 230 ℃; flame retardance: UL-V0 level; the copper clad laminate 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 a high-frequency high-speed copper clad laminate.
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 the benzoxazine resin containing double bonds and the modified polyphenyl ether resin to form a prepolymer, a large number of ether bonds are introduced into the system, so that the system can obtain a low dielectric constant and low dielectric loss, the heat resistance and rigidity of the system can be effectively improved by the introduced large number of benzene ring structures, and the flame retardance of the system is effectively improved by the C-N synergistic effect of the introduced nitrogen elements;
(2) in the modified carbon hydrogen-DCPD epoxy composite material copper-clad plate, an oxazine ring containing double-bond benzoxazine in the formula is subjected to ring-opening crosslinking curing with DCPD epoxy resin, and an epoxy group is introduced into a system, so that the bonding force between the system and a base material is greatly increased, the peel strength is more than or equal to 0.9N/m, and meanwhile, the system has better dielectric property by utilizing a dicyclopentadiene structure in DCPD epoxy;
(3) 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;
(4) 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;
(5) the technical performance of the modified carbon-hydrogen-DCPD epoxy composite copper-clad plate (prepared) is as follows: the dielectric constant is less than or equal to 3.40; dielectric loss is less than or equal to 0.003; the water absorption is less than or equal to 0.15 percent; the peel strength is more than or equal to 1.0N/m; the glass transition temperature Tg is more than or equal to 230 ℃; flame retardance: UL-V0 level; the copper clad laminate 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 a high-frequency high-speed copper clad laminate;
(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: 1) adding 50-200 parts by mass of hydrocarbon resin, 50 parts by mass of a resin mixture of double-bond benzoxazine resin and modified polyphenyl ether resin and 80-230 parts by mass of a solvent A (1) 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 (2) into a reactor II, heating to 30-60 ℃, stirring for dissolving and transparentizing to prepare 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 to be 20-100 ml/min, the feeding speed of the liquid material B is set to be 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 10-50 ℃ for discharging, putting into a vacuum tank with the temperature of 10-60 ℃ and pumping out part of a 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 consumption (unit: kg) and process parameter table for preparing modified hydrocarbon resin
Figure BDA0002344380320000081
Figure BDA0002344380320000091
Note: in the table, hydrocarbon resin i: ricon 181; a hydrocarbon resin II: SODA B-1000; hydrocarbon resin III: ricon 142;
modified polyphenylene ether resin i: sabioc SA9000, polyphenylene ether resin ii: asahi-converted styrene-terminated modified polyphenylene ether resin.
Formula of second part modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate combined feed liquid
Preparing modified hydrocarbon resin prepolymer in the mass ratio: DCPD epoxy 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 carbon-hydrogen-DCPD epoxy composite copper-clad plate combined material liquid, and uniformly mixing.
Table 2: the formula raw materials of the modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate combined material liquid are measured (unit: kg):
Figure BDA0002344380320000092
Figure BDA0002344380320000101
the preparation method of the modified carbon-hydrogen-DCPD epoxy composite copper-clad plate combined feed liquid of the 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;
the preparation of the modified carbon-hydrogen-DCPD epoxy composite copper-clad plate comprises the following steps: cutting and superposing the modified carbon-hydrogen-DCPD epoxy composite 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 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 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 carbon-hydrogen-DCPD epoxy composite prepreg and the metal copper foil;
the comparison of partial technical performances of the modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate prepared by the invention and a comparison plate is shown in the following table 3:
table 3: the modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate is compared with a comparative plate in part of technical performances:
Figure BDA0002344380320000111
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.
(6) Flame retardancy
The standard was determined with reference to UL 94.
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, better flame retardancy, 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 resin mixture of a double-bond-containing benzoxazine resin/modified polyphenylene ether resin, 1 part by mass of an initiator A and 110 parts by mass of a solvent A through a microchannel reactor, and removing part of the solvent.
Example 4:
a modified hydrocarbon resin prepolymer is prepared by mixing and reacting 200 parts by mass of a hydrocarbon resin, 50 parts by mass of a resin mixture of a double-bond benzoxazine resin/modified polyphenylene ether resin, 5 parts by mass of an initiator A and 280 parts by mass of a solvent A through a microchannel reactor, and removing part of the solvent.
Example 5:
a modified hydrocarbon resin prepolymer is prepared by mixing and reacting 125 parts by mass of a hydrocarbon resin, 50 parts by mass of a resin mixture of a double-bond benzoxazine resin/modified polyphenylene ether resin, 3 parts by mass of an initiator A and 195 parts by mass of a solvent A through a microchannel reactor, and removing part of the solvent.
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 resin mixture containing double-bond benzoxazine resin/modified polyphenyl ether resin and 80 parts by mass of a solvent A (1) into a mixing tank I, heating to 30 ℃, stirring and 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 (2) into a mixing tank II, heating to 30 ℃, stirring for dissolving (transparent), and preparing a liquid material B for later use;
and thirdly, connecting the liquid material A and the liquid material B into a microchannel reactor with the temperature set to be 80 ℃ by two feeding pipes, wherein the inner diameter of each feeding pipe is 3mm, setting (namely controlling) 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 liquid material A and the liquid material B to 10 ℃ in a cooling pipe (of the microchannel reactor), discharging, putting the liquid material A into a vacuum tank with the temperature of 10 ℃ and pumping out part of the solvent A to ensure that the solid content 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 200 parts by mass of hydrocarbon resin, 50 parts by mass of a resin mixture containing double-bond benzoxazine resin/modified polyphenylene ether resin and 230 parts by mass of a solvent A (1) into a mixing tank, heating to 60 ℃, stirring and 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 (2) into a mixing tank II, heating to 60 ℃, stirring for dissolving (transparent), and preparing a liquid material B for later use;
and thirdly, connecting the liquid material A and the 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, setting (namely controlling) 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 (of the microchannel reactor), discharging, putting the mixture into a vacuum tank with the temperature of 60 ℃, pumping out part of the solvent A, and enabling the solid content to be 72%, thereby obtaining the modified hydrocarbon resin prepolymer.
Example 8:
a preparation method of a modified hydrocarbon resin prepolymer comprises the following steps:
firstly, adding 125 parts by mass of hydrocarbon resin, 50 parts by mass of a resin mixture containing double-bond benzoxazine resin/modified polyphenylene ether resin and 155 parts by mass of a solvent A (1) into a mixing tank, 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 (2) into a mixing tank II, heating to 45 ℃, stirring for dissolving (transparent), and preparing a liquid material B for later use;
and thirdly, connecting the liquid material A and the liquid material B into a microchannel reactor with the temperature set to be 115 ℃ by using two feeding pipes, wherein the inner diameters of the feeding pipes are both 3mm, setting (namely controlling) 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 30 ℃ in a cooling pipe (of the microchannel reactor), discharging, putting the mixture into a vacuum tank with the temperature of 35 ℃ and pumping out part of the solvent A to ensure that the solid content is 70 percent, and thus obtaining 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.;
the resin mixture of the double-bond-containing benzoxazine resin/modified polyphenyl ether resin comprises the following components in percentage by mass: modified polyphenylene ether resin ═ 1: 1-9; the production enterprises of benzoxazine resin containing double bonds have eastern wood science and technology; the manufacturers of modified polyphenylene ether resins include sabik, asahi chemical compounds, 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 embodiments 6 to 8: the double bond-containing benzoxazine resin is one or a mixture of more than two of compounds with chemical structural formulas shown as the following formulas:
①
Figure BDA0002344380320000141
in formula (I): r1Is composed of
Figure BDA0002344380320000142
And k is 0 or 1, R2Is H, C1～C12Alkyl, vinyl, allyl, phenyl, amino, nitro, naphthyl or cyclohexyl of (a); r3Is H, -CH3；
②
Figure BDA0002344380320000151
Formula (II): r4Is vinyl, allyl or a structure of formula (III) R5is-CH2-、-C(CH3)2-、-SO2、-O-、-CO-；
③
Figure BDA0002344380320000152
Formula (III): r6H, allyl, nitro, alkynyl and the like;
④
Figure BDA0002344380320000153
in the formula (IV): r7is-CH2-、-SO2，R8is-CH2-、-C2H4-、-O-CH2-；
In examples 6 to 8 above: the chemical structural formula of the modified polyphenyl ether resin is represented by the formula (v):
⑤
Figure BDA0002344380320000154
in the formula: n is 5 to 20, R9/R10The molecular structure of the compound is a molecular structure of which the terminal contains an active group of allyl, vinyl or styryl.
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 carbon-hydrogen-DCPD epoxy composite material copper-clad plate is characterized in that the mass ratio of the modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate is as follows: DCPD epoxy 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 carbon-hydrogen-DCPD epoxy composite material copper-clad plate is characterized in that the mass ratio of the modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate is as follows: DCPD epoxy 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 carbon-hydrogen-DCPD epoxy composite material copper-clad plate is characterized in that the mass ratio of the modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate is as follows: DCPD epoxy 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 structure of the DCPD epoxy resin (namely dicyclopentadiene phenol type epoxy resin) is as follows:
⑥
Figure BDA0002344380320000171
in the formula, n is an integer of 1-10;
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 copper foil has no limitation on the thickness.
In the above embodiments 9 to 11: the modified carbon-hydrogen-DCPD epoxy composite copper-clad plate has excellent comprehensive performance and the technical performance is as follows: the dielectric constant is less than or equal to 3.40; dielectric loss is less than or equal to 0.003; the water absorption is less than or equal to 0.15 percent; the peel strength is more than or equal to 0.8N/m; the glass transition temperature Tg is more than or equal to 230 ℃; flame retardance: UL-V0 level; the copper clad laminate 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 a high-frequency high-speed copper clad laminate.
Example 12:
a preparation method of a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate comprises the following steps:
a. preparing a modified carbon hydrogen-DCPD epoxy composite prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: DCPD epoxy 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 DCPD epoxy resin, the inorganic filler, the initiator C, the accelerator B and the solvent B to prepare modified hydrocarbon-DCPD epoxy composite copper-clad plate combined feed liquid, putting the reinforcing material into the modified hydrocarbon-DCPD epoxy composite copper-clad plate combined feed liquid (fully) for soaking, then taking out, and baking at 120 ℃ for 10min to prepare a modified hydrocarbon-DCPD epoxy composite prepreg;
b. preparing a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate:
cutting and superposing the modified carbon-hydrogen-DCPD epoxy composite prepreg and the metal copper foil according to the length, width and thickness requirements, then placing the prepreg and the metal copper foil in a hot press, keeping the heating rate at 1 ℃/min, pressing for 3 hours at the pressure of 0.2MPa and the temperature of 80 ℃ after reaching the temperature (namely the temperature of 80 ℃), then continuing heating, keeping the heating rate at 1 ℃/min, pressing for 6 hours at the pressure of 2MPa and the temperature of 180 ℃ after reaching the temperature (namely the temperature of 180 ℃), and thus obtaining the modified carbon-hydrogen-DCPD epoxy composite copper-clad plate.
Example 13:
a preparation method of a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate comprises the following steps:
a. preparing a modified carbon hydrogen-DCPD epoxy composite prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: DCPD epoxy resin: inorganic filler: an initiator C: accelerator B: solvent B ═ 90: 30: 100: 1: 1: 86, uniformly mixing the modified hydrocarbon resin prepolymer, the DCPD epoxy resin, the inorganic filler, the initiator C, the accelerator B and the solvent B to prepare modified hydrocarbon-DCPD epoxy composite copper-clad plate combined feed liquid, putting the reinforcing material into the modified hydrocarbon-DCPD epoxy composite copper-clad plate combined feed liquid (fully) for dipping, then taking out, and baking at 185 ℃ for 1min to prepare a modified hydrocarbon-DCPD epoxy composite prepreg;
b. preparing a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate:
cutting and superposing the modified carbon-hydrogen-DCPD epoxy composite prepreg and the metal copper foil according to the length, width and thickness requirements, then placing the prepreg and the metal copper foil in a hot press, keeping the heating rate at 3 ℃/min, pressing for 1 hour at the pressure of 1MPa and the temperature of 150 ℃ after reaching the temperature (namely the temperature of 150 ℃), then continuing heating, keeping the heating rate at 3 ℃/min, pressing for 1 hour at the pressure of 7MPa and the temperature of 250 ℃ after reaching the temperature (namely the temperature of 250 ℃), and thus obtaining the modified carbon-hydrogen-DCPD epoxy composite copper-clad plate.
Example 14:
a preparation method of a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate comprises the following steps:
a. preparing a modified carbon hydrogen-DCPD epoxy composite prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: DCPD epoxy resin: inorganic filler: an initiator C: accelerator B: solvent B ═ 90: 20: 70: 0.06: 0.06: 79, uniformly mixing the modified hydrocarbon resin prepolymer, the DCPD epoxy resin, the inorganic filler, the initiator C, the accelerator B and the solvent B to prepare a modified hydrocarbon-DCPD epoxy composite copper-clad plate combined material liquid, putting the reinforcing material into the modified hydrocarbon-DCPD epoxy composite copper-clad plate combined material liquid for (sufficient) soaking, then taking out, and baking at the temperature of 155 ℃ for 6min to prepare a modified hydrocarbon-DCPD epoxy composite prepreg;
b. preparing a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate:
cutting and superposing the modified carbon-hydrogen-DCPD epoxy composite prepreg and the metal copper foil according to the length, width and thickness requirements, then placing the prepreg and the metal copper foil in a hot press, keeping the heating rate at 2 ℃/min, pressing for 2 hours at the pressure of 0.6MPa and the temperature of 115 ℃ after reaching the temperature (namely the temperature of 115 ℃), then continuing heating, keeping the heating rate at 2 ℃/min, pressing for 3.5 hours at the pressure of 5MPa and the temperature of 215 ℃ after reaching the temperature (namely the temperature of 215 ℃), and thus obtaining the modified carbon-hydrogen-DCPD epoxy composite copper-clad plate.
Example 15:
a preparation method of a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate comprises the following steps:
a. preparing a modified carbon hydrogen-DCPD epoxy composite prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: DCPD epoxy resin: inorganic filler: an initiator C: accelerator B: solvent B ═ 90: 16: 50: 0.04: 0.03: 77, uniformly mixing the modified hydrocarbon resin prepolymer, the DCPD epoxy resin, the inorganic filler, the initiator C, the accelerator B and the solvent B to prepare modified hydrocarbon-DCPD epoxy composite copper-clad plate combined feed liquid, putting the reinforcing material into the modified hydrocarbon-DCPD epoxy composite copper-clad plate combined feed liquid (fully) for dipping, then taking out, and baking at 135 ℃ for 3min to prepare a modified hydrocarbon-DCPD epoxy composite prepreg;
b. preparing a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate:
cutting and superposing the modified carbon-hydrogen-DCPD epoxy composite 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 1.5 ℃/min, pressing for 2 hours at the pressure of 0.4MPa and the temperature of 95 ℃ after reaching the temperature (namely the temperature of 95 ℃), then continuing heating, keeping the heating rate at 1.5 ℃/min, pressing for 4.5 hours at the pressure of 3MPa and the temperature of 195 ℃ after reaching the temperature (namely the temperature of 195 ℃), and thus obtaining the modified carbon-hydrogen-DCPD epoxy composite copper clad plate.
Example 16:
a preparation method of a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate comprises the following steps:
a. preparing a modified carbon hydrogen-DCPD epoxy composite prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: DCPD epoxy 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 DCPD epoxy resin, the inorganic filler, the initiator C, the accelerator B and the solvent B, uniformly mixing to prepare a modified hydrocarbon-DCPD epoxy composite copper-clad plate combined material liquid, putting the reinforcing material into the modified hydrocarbon-DCPD epoxy composite copper-clad plate combined material liquid (fully) for dipping, then taking out, and baking at 175 ℃ for 4min to prepare a modified hydrocarbon-DCPD epoxy composite prepreg;
b. preparing a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate:
cutting and superposing the modified carbon-hydrogen-DCPD epoxy composite 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 2.5 ℃/min, pressing for 2 hours at the pressure of 0.8MPa and the temperature of 140 ℃ after reaching the temperature (namely the temperature of 140 ℃), then continuing heating, keeping the heating rate at 2.5 ℃/min, pressing for 2.5 hours at the pressure of 6MPa and the temperature of 235 ℃ after reaching the temperature (namely the temperature of 235 ℃), and thus obtaining the modified carbon-hydrogen-DCPD epoxy composite 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 chemical structure of the DCPD epoxy resin (namely dicyclopentadiene phenol type epoxy resin, production enterprises have Shandong Laiwu Runda, Country chemical industry, Guangzhou Taiji new material and the like) is represented by the following formula (i):
⑥
Figure BDA0002344380320000201
in the formula, n is an integer of 1-10;
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 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 12 to 16: the prepared modified carbon-hydrogen-DCPD epoxy composite copper-clad plate has excellent comprehensive performance and the technical performance is as follows: the dielectric constant is less than or equal to 3.40; dielectric loss is less than or equal to 0.003; the water absorption is less than or equal to 0.15 percent; the peel strength is more than or equal to 0.8N/m; the glass transition temperature Tg is more than or equal to 230 ℃; flame retardance: UL-V0 level; the copper clad laminate 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 a high-frequency high-speed copper clad laminate.
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, speed, etc.) and the amounts of the components in each step are within ranges, 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 (4)

1. A preparation method of modified hydrocarbon resin prepolymer is characterized by comprising the following steps:
firstly, adding 50-200 parts by mass of hydrocarbon resin, 50 parts by mass of a resin mixture containing double-bond benzoxazine resin/modified polyphenyl ether resin and 80-230 parts by mass of a solvent A into a mixing tank I, 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 into a mixing tank II, heating to 30-60 ℃, stirring and dissolving to prepare 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, wherein the inner diameters of the feeding pipes are both 3mm, the feeding speed of the liquid material A is set to be 20-100 ml/min, the feeding speed of the liquid material B is set to be 2-10 ml/min, the liquid material A and the liquid material B are subjected to mixed reaction in a microchannel reactor channel, the liquid material A and the liquid material B enter a cooling pipe to be cooled to 10-50 ℃ for discharging, the liquid material A is placed into a vacuum tank with the temperature of 10-60 ℃ to extract part of solvent A, and the solid content is 68-72%, so that the modified hydrocarbon resin prepolymer is prepared;
the hydrocarbon resin is one or a mixture of more than two of polybutadiene resin, polyisobutylene diene resin, polypentadiene resin, styrene-butadiene copolymer, styrene-isobutylene diene copolymer, styrene-divinylbenzene copolymer, polystyrene, 2-methyl polystyrene, 3-methyl polystyrene, 4-methyl polystyrene, 2, 4-diisopropyl polystyrene, 2, 4-dimethyl polystyrene, ethylene propylene terpolymer and cycloolefin copolymer;
the resin mixture of the double-bond-containing benzoxazine resin/modified polyphenyl ether resin comprises the following components in percentage by mass: modified polyphenylene ether 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;
the double bond-containing benzoxazine resin is one or a mixture of more than two of compounds with chemical structural formulas shown as the following formulas:
①
Figure FDA0003235509730000021
in formula (I): r1Is composed of
Figure FDA0003235509730000022
And k is 0 or 1, R2Is H, C1～C12Alkyl, vinyl, allyl, phenyl, amino, nitro, naphthyl or cyclohexyl of (a); r3Is H, -CH3；
②
Figure FDA0003235509730000023
Formula (II): r4Is vinyl, allyl or a structure of formula (III) R5is-CH2-、-C(CH3)2-、-SO2、-O-、-CO-；
③
Figure FDA0003235509730000024
Formula (III): r6H, allyl, nitro, alkynyl;
④
Figure FDA0003235509730000025
in the formula (IV): r7is-CH2-、-SO2，R8is-CH2-、-C2H4-、-O-CH2-；
The chemical structural formula of the modified polyphenyl ether resin is represented by the formula (v):
⑤
Figure FDA0003235509730000026
in the formula: n is 5 to 20, R9/R10The molecular structure of the compound is a molecular structure of which the terminal contains an active group of allyl, vinyl or styryl.
2. A preparation method of a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate is characterized by comprising the following steps:
a. preparing a modified carbon hydrogen-DCPD epoxy composite prepreg:
according to the mass ratio, modified hydrocarbon resin prepolymer: DCPD epoxy resin: inorganic filler: an initiator C: accelerator B: solvent B ═ 90: 10-30: 40-100: 0.01-1: 0.01-1: 73-86 taking the modified hydrocarbon resin prepolymer, the DCPD epoxy resin, the inorganic filler, the initiator C, the accelerator B and the solvent B, uniformly mixing to prepare a modified hydrocarbon-DCPD epoxy composite copper-clad plate combined feed liquid, putting the reinforcing material into the modified hydrocarbon-DCPD epoxy composite copper-clad plate combined feed liquid, dipping, taking out, and baking at the temperature of 120-185 ℃ for 1-10 min to prepare a modified hydrocarbon-DCPD epoxy composite prepreg;
b. preparing a modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate:
cutting and superposing the modified carbon-hydrogen-DCPD epoxy composite 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 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, pressing for 1-6 hours at the pressure of 2-7 MPa and the temperature of 180-250 ℃ after reaching the temperature, and thus obtaining the modified carbon-hydrogen-DCPD epoxy composite copper clad plate;
the chemical structure of the DCPD epoxy resin is as follows:
⑥
Figure FDA0003235509730000031
in the formula, n is an integer of 1-10;
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;
the preparation method of the modified hydrocarbon resin prepolymer comprises the following steps:
firstly, adding 50-200 parts by mass of hydrocarbon resin, 50 parts by mass of a resin mixture containing double-bond benzoxazine resin/modified polyphenyl ether resin and 80-230 parts by mass of a solvent A into a mixing tank I, 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 into a mixing tank II, heating to 30-60 ℃, stirring and dissolving to prepare 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, wherein the inner diameters of the feeding pipes are both 3mm, the feeding speed of the liquid material A is set to be 20-100 ml/min, the feeding speed of the liquid material B is set to be 2-10 ml/min, the liquid material A and the liquid material B are subjected to mixed reaction in a microchannel reactor channel, the liquid material A and the liquid material B enter a cooling pipe to be cooled to 10-50 ℃ for discharging, the liquid material A is placed into a vacuum tank with the temperature of 10-60 ℃ to extract part of solvent A, and the solid content is 68-72%, so that the modified hydrocarbon resin prepolymer is prepared;
the hydrocarbon resin is one or a mixture of more than two of polybutadiene resin, polyisobutylene diene resin, polypentadiene resin, styrene-butadiene copolymer, styrene-isobutylene diene copolymer, styrene-divinylbenzene copolymer, polystyrene, 2-methyl polystyrene, 3-methyl polystyrene, 4-methyl polystyrene, 2, 4-diisopropyl polystyrene, 2, 4-dimethyl polystyrene, ethylene propylene terpolymer and cycloolefin copolymer;
the resin mixture of the double-bond-containing benzoxazine resin/modified polyphenyl ether resin comprises the following components in percentage by mass: modified polyphenylene ether 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;
the double bond-containing benzoxazine resin is one or a mixture of more than two of compounds with chemical structural formulas shown as the following formulas:
①
Figure FDA0003235509730000051
in formula (I): r1Is composed of
Figure FDA0003235509730000052
And k is 0 or 1, R2Is H, C1～C12Alkyl, vinyl, allyl, phenyl, amino, nitro, naphthyl or cyclohexyl of (a); r3Is H, -CH3；
②
Figure FDA0003235509730000053
Formula (II): r4Is vinyl, allyl or a structure of formula (III) R5is-CH2-、-C(CH3)2-、-SO2、-O-、-CO-；
③
Figure FDA0003235509730000054
Formula (III): r6H, allyl, nitro, alkynyl;
④
Figure FDA0003235509730000055
in the formula (IV): r7is-CH2-、-SO2，R8is-CH2-、-C2H4-、-O-CH2-；
The chemical structural formula of the modified polyphenyl ether resin is represented by the formula (v):
⑤
Figure FDA0003235509730000061
in the formula: n is 5 to 20, R9/R10The molecular structure of the compound is a molecular structure of which the terminal contains an active group of allyl, vinyl or styryl.
3. The preparation method of the modified carbon-hydrogen-DCPD epoxy composite copper-clad plate according to claim 2, which is characterized in that: the reinforcing material is any one of organic synthetic fiber, natural fiber, organic fabric, inorganic fabric.
4. The preparation method of the modified carbon-hydrogen-DCPD epoxy composite copper-clad plate according to claim 2 or 3, which is characterized in that: the technical performance of the prepared modified carbon-hydrogen-DCPD epoxy composite material copper-clad plate is as follows: the dielectric constant is less than or equal to 3.40; dielectric loss is less than or equal to 0.003; the water absorption is less than or equal to 0.15 percent; the peel strength is more than or equal to 0.8N/m; the glass transition temperature Tg is more than or equal to 230 ℃; flame retardance: UL-V0 grade.
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