CN115093603B - PCB dielectric material for signal high-frequency high-speed propagation and preparation method thereof - Google Patents
PCB dielectric material for signal high-frequency high-speed propagation and preparation method thereof Download PDFInfo
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 94
- 238000005187 foaming Methods 0.000 claims abstract description 52
- 230000032683 aging Effects 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 238000007336 electrophilic substitution reaction Methods 0.000 claims abstract description 11
- 150000003254 radicals Chemical class 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 239000004088 foaming agent Substances 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 10
- 238000007347 radical substitution reaction Methods 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003063 flame retardant Substances 0.000 abstract description 11
- 238000007385 chemical modification Methods 0.000 abstract description 9
- 238000000465 moulding Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000007348 radical reaction Methods 0.000 abstract 1
- 239000007783 nanoporous material Substances 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000004048 modification Effects 0.000 description 17
- 238000012986 modification Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 12
- 230000031709 bromination Effects 0.000 description 9
- 238000005893 bromination reaction Methods 0.000 description 9
- 238000005658 halogenation reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- -1 arylalkyl acid chloride Chemical compound 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 230000026030 halogenation Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011799 hole material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 238000010099 solid forming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005140 aralkylsulfonyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a PCB dielectric material for signal high-frequency high-speed propagation and a preparation method thereof, belonging to the technical field of supercritical foaming. The patent uses PPO as a production example and supercritical CO 2 As a physical foaming agent, the PPO is subjected to supercritical solid-state molding by adopting an intermittent foaming process to prepare the PPO micro-nano-pore foaming material, and the secondary structure of the material is limited by an irradiation crosslinking mode, so that the material is subjected to chemical modification. The PPO micro-nano porous foaming material is subjected to end capping reaction and free radical reaction to prepare the anti-thermal oxidation aging micro-nano porous foaming material, and the PPO anti-thermal oxidation aging micro-nano porous foaming material is subjected to electrophilic substitution reaction to finally obtain the ultra-high wave-transparent and low-loss anti-thermal oxidation aging flame-retardant PCB dielectric substrate.
Description
Technical Field
The invention relates to a PCB board for signal high-frequency high-speed propagation and a preparation method thereof, belonging to the technical field of PCB and supercritical foaming.
Background
As electronic information technology has moved into the high-speed era, the market has placed higher demands on the high-frequency and high-speed propagation of signals within PCBs. The dielectric material is used as an important component of the PCB, and various performance indexes of the dielectric material are key to influence the high-frequency and high-speed propagation of signals and various performances of the PCB. According to shannon's theorem, dielectric materials must meet ultra-low dielectric and low loss in order to meet the propagation of signals at high frequencies and high speeds; in order to meet the processing requirements of the PCB, the dielectric material needs to have a certain mechanical strength at high temperature to maintain the structural integrity; meanwhile, the development of the 5G technology obviously improves the number of 5G base stations, shortens the distance between the base stations, and obviously meets the current requirement of 5G development, so that the dielectric material needs to have high temperature resistance and self-flame retardance. The polyphenyl ether (namely poly (2, 6-dimethyl-1, 4-phenylene ether) (PPO) or polyphenyl ether polymer alloy (such as PPO/Polystyrene (PS) alloy) has the characteristics of low dielectric constant (2.6, dielectric loss of 0.005) and high performance (excellent mechanical property, heat resistance and flame retardance), and the micro-nano pore structure obtained by the supercritical solid forming process endows the polyphenyl ether with ultralow dielectric constant (1.1) and ultralow dielectric loss (below 0.0011), thereby meeting the requirements of high-speed transmission of signals and fidelity of signals under high frequency (3 GHz-50 GHz). However, the heat resistance of the PPO micro-nano porous material is slightly lower than that of the PPO nano composite material, and the PPO micro-nano porous material is blended and modified with other system polymers, so that the rigidity, the heat resistance and the flame retardance of the PPO micro-nano porous material are further weakened. Therefore, how to improve the temperature resistance, flame retardance and chemical stability of the PPO micro-nano porous material becomes a current urgent problem to be solved under the premise of meeting the requirements of low dielectric property, low loss and easiness in processing.
Disclosure of Invention
The patent uses PPO as a production example and supercritical CO 2 As a physical foaming agent, performing supercritical solid-state molding on PPO by adopting an intermittent foaming process to prepare a high-performance PPO foaming material with a micro-nano pore structure, and performing irradiation crosslinking modification on the PPO micro-nano pore material to generate a microscopic crosslinked network structure to limit the movement of a molecular chain, so that the material maintains a cell structure under the condition of chemical reagent modification and the heat resistance of the material is improved; the PPO micro-nano porous foaming material is subjected to end capping reaction so as to improve the thermal oxidative aging resistance of the material, and halogenated electrophilic substitution reaction is performed on the material so as to prepare the thermal oxidative aging resistant flame retardant micro-nano porous foaming material, so that the ultra-high wave-transparent and low-loss thermal oxidative aging resistant flame retardant PCB dielectric substrate is finally obtained.
The PCB dielectric material for high-frequency and high-speed signal propagation is a porous foaming material, and the porous foaming material has a structure shown in the following formula:
wherein R is 1 And R is 2 Is a capping substituent; for example, it may be alkyl, cycloalkyl, aryl or arylalkyl acid chloride; dialkyl, cycloalkyl, aryl or arylalkyl sulfates; alkyl, cycloalkyl, aryl or arylalkyl sulfonyl chloride; alkyl, cycloalkyl, aryl, or arylalkyl anhydrides, and the like.
R 3 Halogen atoms, such as F, cl, br and I.
The pore diameter of the porous foaming material is 0.5-50um, and the density of the pores is 1 multiplied by 10 6 ～1×10 11 Individual/cm 3 。
The preparation method of the porous foaming material comprises the following steps:
step 1, taking PPO or PPO alloy as a raw material, and obtaining a foaming material by a supercritical foaming method;
step 2, carrying out irradiation crosslinking on the foaming material at different irradiation doses to obtain a crosslinked modified foaming material;
step 3, carrying out free radical substitution reaction treatment such as halogenation or chlorosulfonation on the crosslinked and modified foaming material obtained in the step 2;
and 4, performing electrophilic substitution reaction treatment on the benzene ring on the crosslinked modified foaming material obtained in the step 3.
The supercritical foaming method in the step 1 adopts supercritical CO 2 Is a physical foaming agent, and is subjected to pressure relief foaming after swelling for 0.1 to 5 hours under the process conditions of 130 to 200 ℃ and 5 to 25 MPa.
The irradiation dose in the step 2 is 10 to 500kGy, preferably 500kGy.
The free radical substitution reaction treatment in the step 3 is to carry out substitution reaction with ethylene oxide under the acid or alkaline condition, the reaction temperature is 20-140 ℃, the reaction time is 5 minutes-2 hours, and the hydrogen atoms on the PPO end group and the methyl are substituted.
The acid is sulfuric acid, acetic acid or perchloric acid; the alkali is trialkylamine, triphenylphosphine and the like.
The electrophilic substitution reaction treatment in the step 4 is as follows: placing the PPO micro-nano porous foaming material with the thermal oxidation aging resistance in a halogen atom environment, wherein the reaction temperature is 20-130 ℃ and the reaction time is 30 minutes-4 hours.
The PCB dielectric material for high-frequency and high-speed signal propagation is applied to a dielectric substrate in a PCB copper-clad plate.
The radical substitution reaction refers to the reaction of substituting hydrogen atoms of alkoxy, alkyl, phenyl, peroxy radicals and halogen atoms. The electrophilic substitution reaction refers to a reaction in which an atom or an atomic group in a compound or an organic polymer molecule is substituted with an electrophile. The substitution reaction (such as halogenation, nitration, sulfonation, friedel-crafts reaction, etc.) on the benzene ring is an electrophilic substitution reaction. The halogenation reaction is carried out by directly carrying out halogenation reaction on the reaction raw material and halogen.
The structural formula of the PPO is shown in figure 1. The PPO methyl and H atoms of the end group can also undergo free radical substitution reactions such as halogenation, chlorosulfonation and the like, and the free radical substitution reactions can replace the methyl and H atoms of the end group so as to improve the thermo-oxidative aging resistance of PPO and the heat resistance of the material, and the reactions are as follows:
wherein C is 2 H 4 O is ethylene oxide.
The benzene ring in the repeating unit has a large pi bond, and the H atom is easy to generate electrophilic substitution reaction with the electron-deficient group. Therefore, halogenation reaction, chloromethylation reaction, sulfonation reaction and the like can occur on the benzene ring. After the halogen element is subjected to halogenation reaction, the steric hindrance of halogen is larger than H, so that the rigidity of a microscopic molecular chain of the material is obviously improved, the temperature resistance of the material is improved, and the flame retardant property of the material is also improved due to the introduction of halogen. The reaction is as follows:
the cross-linked network obtained by the cross-linking reaction can limit the sliding of molecular chains, so that the microstructure of the material is kept stable when the material is subjected to chemical modification, and the structure of a macroscopic object is further kept stable, as shown in figure 2.
The polymer can be divided into a primary structure, a secondary structure and a tertiary structure, wherein the primary structure is the arrangement of atomic groups on a single molecular chain, and the secondary structure is the space structure of the whole molecular chain. The foaming material is subjected to irradiation crosslinking modification, so that a crosslinking network is formed inside the material, and the movement of molecular chains is limited, so that the material is soaked in an organic solvent and the like without changing the structure and being corroded. The patent innovatively proposes a molecular structure design (carrying out crosslinking modification and chemical modification on the structure of a PPO micro-nano pore material), combines a cell structure design (micro-nano pore structure) and a multiphase structure (multiphase high polymer alloy, filler phase and air phase), selects PPO, modified high polymer alloy of the PPO and other polymers with the structure, and firstly regulates and controls the micro-nano pore structure of the material through a supercritical solid forming process; secondly, the obtained micro-nano porous material is subjected to irradiation crosslinking modification to generate a microscopic crosslinked network structure to limit the movement of a molecular chain, so that the material maintains a cell structure and improves the heat resistance of the material under the condition of chemical reagent modification; then, the crosslinked modified micro-nano pore foaming material is subjected to esterification or etherification and other acylation end-capping reactions to replace hydrogen atoms on the terminal group and methyl so as to improve the thermal oxygen stability of the material; finally, H on the benzene ring is replaced by halogenation reaction so as to improve the rigidity, heat resistance and flame retardance of the material.
Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) The material is modified after foaming molding, so that the processing cost is obviously reduced, and the equipment pressure is reduced;
(2) The micro-nano porous material has larger foaming multiplying power and uniform cell size, and a large amount of air is introduced so as to obviously reduce dielectric constant and dielectric loss;
(3) The crosslinking modification of the micro-nano pore material ensures the chemical reagent resistance of the material and improves the heat resistance of the material; the chemical modification obviously improves the rigidity, heat resistance, thermal oxygen stability and chemical stability of the material, and the obtained material as a dielectric material not only meets the high-frequency and high-speed transmission of signals, but also meets the processing requirements of a PCB and the use requirements of the material in various bad environments.
Drawings
FIG. 1 is a structural formula of PPO;
FIG. 2 is a molecular chain variation diagram of a cross-linked modified PPO micro-nano porous material;
FIG. 3 is a solution of non-crosslinked modified and crosslinked modified PPO micro-nano porous material in toluene as an organic solvent for 1 hour;
FIG. 4 is a cell structure diagram of the PPO micro-nano porous material after molecular structure modification;
FIG. 5 is a DSC curve of a PPO micro-nano porous material before and after chemical modification;
fig. 6 is a diagram of two vertical combustion experiments, wherein (1) (2) (3) (4) is the first time, and (a) (b) (c) (d) is the second time.
Detailed Description
Example 1
Firstly, PPO particles are dried in a vacuum oven at 100 ℃ for 6 hours (PPO has extremely low water absorption rate because of no polar group and can not be dried), then a vacuum film pressing machine is adopted to press the resin particles into a plate, and then the plate is placed in a mould pressing foaming kettle to obtain supercritical CO 2 And swelling for 1.5 hours at 170 ℃ under 17MPa, and then decompressing and foaming to obtain the PPO micro-nano porous foaming material. And standing the PPO micro-nano porous foaming material in the air at room temperature for 24 hours to stabilize the structure of the foaming material. And (3) respectively carrying out irradiation crosslinking on the micro-nano porous foaming sheet material under the irradiation doses of 10kGy, 100kGy and 500kGy to obtain a crosslinked and modified PPO micro-nano porous foaming material. And (3) putting the crosslinked PPO foaming material, sulfuric acid and ethylene oxide into a reaction kettle for substitution reaction, wherein the reaction temperature is 120 ℃, and the reaction time is 30 minutes, so as to substitute hydrogen atoms on PPO end groups and methyl groups, thereby obtaining the heat-oxidative aging-resistant PPO micro-nano pore foaming material. Placing the PPO micro-nano pore foaming material with heat and oxidation aging resistance in Br 2 Environmental (bromine gas) internal brominating materialThe reaction temperature is 100 ℃ and the reaction time is 2 hours. And H on the PPO benzene ring is replaced to obtain the heat-oxidation aging resistant flame-retardant PPO micro-nano porous foaming material. The reaction temperature does not exceed the glass transition temperature of the PPO micro-nano porous material, and the reaction is a nanoscale substitution reaction and does not influence the microscopic molecular chain structure, so that the overall structure of the material is not changed. The materials are respectively subjected to Scanning Electron Microscope (SEM) test to observe microscopic cell structures, differential Scanning Calorimetry (DSC) test to characterize the heat resistance of the materials, thermo-oxidative aging test to characterize the heat resistance of the materials and vertical combustion test.
The pore diameter of the porous foaming material is 0.5-50um, and the density of the pores is 1 multiplied by 10 6 ～1×10 11 Individual/cm 3 。
Comparative example 1
The difference from example 1 is that: the foaming material is not subjected to substitution reaction treatment of ethylene oxide.
Comparative example 2
The difference from example 1 is that: the foam was not brominated.
Comparative example 3
The difference from example 1 is that: the foam was not subjected to ethylene oxide and bromination treatments.
Microscopic cell structures were analyzed by Scanning Electron Microscopy (SEM), thermal properties of the materials were tested by DSC testing, thermal oxidative aging resistance of the materials was analyzed by thermal oxidative aging testing (materials were hot air aged by a forced air oven, each material was heat cycled for 24 hours at 10 ℃ below the glass transition temperature), and flame retardant properties of the materials were analyzed by vertical burn tests.
FIG. 3 shows the dissolution of PPO micro-nano porous material which is not modified by irradiation crosslinking and is modified by irradiation crosslinking with different dosages in toluene as an organic solvent for one hour. By the principle of similar miscibility, PPO is soluble in toluene. The PPO micro-nano pore material which is not modified by cross-linking in fig. 3 is mostly dissolved in toluene, so that the material structure cannot be maintained; the PPO modified by low-dose irradiation crosslinking is partially dissolved in toluene, and the material structure cannot be completely maintained; and the PPO micro-nano porous material subjected to high-dose (500 KGy) irradiation crosslinking can maintain the structure of the material in toluene. Therefore, the crosslinking limits the microscopic molecular chain structure of the material, maintains the structure of the material, and can resist chemical reagents so as to carry out chemical modification.
FIG. 4 is a diagram showing the structure of the cells of the PPO micro-nano porous material after modification of the molecular structure, wherein the four different modification conditions are basically consistent in the structure of the cells of the material, and the cross-linking modification and chemical modification do not change the structure of molecular chains, so that the structure of the cells is not changed. Cell pore size at the micrometer scale, uniform pore size and high pore density, cell parameter data are shown in table 1 below. The pore diameters of the cells are uniform, so that the signal loss of the signal due to skin effect is weakened; the pore diameter is smaller, the number of the cells is more, the better mechanical property of the material is ensured, and the scattering and reflection loss in the electromagnetic wave transmission process is reduced; the larger foaming multiplying power leads the content of air introduced into the material to be larger, and greatly reduces the dielectric constant and the loss tangent angle of the material. Table 2 shows the electrical property data of the materials after thermal oxidative aging of the various modified PPO materials, and the dielectric constant, dielectric loss and resistivity of the materials after aging are improved due to structural changes. The PPO micro-nano porous material substituted by ethylene oxide has better thermal-oxidative aging resistance, and the material substituted by bromination only slightly improves the thermal-oxidative aging resistance because the hydrogen atoms on the methyl groups are replaced by chlorine atoms. Whereas PPO micro-nano Kong Cailiao, which was re-brominated after ethylene oxide substitution, exhibited the best resistance to thermal oxidative aging.
TABLE 1 cell structure of PPO micro-nano porous material
TABLE 2 Table of electrical properties of materials before and after chemical modification and after thermal oxidative aging
| Micro-nano pore material | Dielectric constant (3 GHz) | Dielectric loss (3 GHz) | Volume resistivity (Ω. M) |
| Example 1 | 1.12 | 0.0011 | 3.7×10 16 |
| Comparative example 1 | 1.10 | 0.00009 | 7.6×10 14 |
| Comparative example 2 | 1.12 | 0.0018 | 2.3×10 16 |
| Comparative example 3 | 1.11 | 0.0011 | 8.2×10 13 |
FIG. 5 is a DSC curve comparison of a PPO micro-nano porous material before chemical modification and a PPO micro-nano porous material after modification, and shows that the glass transition temperature of an unmodified PPO micro-nano porous material is the lowest, and the glass transition temperature of the PPO micro-nano porous material after bromination modification is lower than that of the PPO micro-nano porous material after epoxidation modification only, because the benzene ring of the PPO can generate electrophilic substitution reaction through bromination, so that the heat resistance of the material is improved, and meanwhile, the methyl on the benzene ring can generate free radical substitution reaction through bromination, so that the heat resistance of the material is reduced, and the electrophilic substitution reaction and the free radical substitution reaction are carried out simultaneously, so that the heat resistance improvement degree of the material is limited. The substitution reaction of ethylene oxide to replace H atom in the end group and methyl can raise the heat resistance and heat oxygen ageing performance of the material, so that the glass transition temperature is raised, while the H atom in benzene ring is not brominated, so that the glass transition temperature is lower than that of the PPO micro-nano pore material chemically modified twice.
Table 2 shows that the material has improved resistance to thermal oxidative aging by introducing ethylene oxide, but also has increased polarity, which increases dielectric loss at high frequencies. The introduction of Br atoms can slightly reduce the dielectric loss of the material.
To determine the flame retardant properties of the modified PPO micro-nano-porous materials, two vertical combustion tests were performed on four PPO micro-nano-porous materials, as shown in fig. 6. The thickness of the sample is 7mm, the first after flame time of the unmodified PPO micro-nano pore material is 2.3s, the second after flame time is 2.8s, the second total time is 5.2s, no drip exists in the two test samples, the flame is quickly self-extinguished, and the V0 level is judged according to the standard. Therefore, the flame retardant effect is excellent. The PPO micro-nano hole material only subjected to bromination modification has the first after-flame time of 1.9s, the second after-flame time of 1.8s, the second afterglow time of 2.5s and the second total time of 4.5s, and the two test samples have no dripping, are rapidly self-extinguished after being separated from fire, and are judged to be V0 level according to the standard. The flame retardant effect is better than that of unmodified PPO micro-nano porous material. The PPO micro-nano hole material modified by the ethylene oxide has the first after-flame time of 2.2s, the second after-flame time of 2.1s, the second afterglow time of 2.7s and the total second time of 4.9s, and the two test samples have no dripping, are rapidly self-extinguished after being separated from fire, and are judged to be V0 level according to the standard. The flame retardant effect of the modified PPO micro-nano porous material is equivalent to that of an unmodified PPO micro-nano porous material. The PPO micro-nano porous material subjected to substitution modification by ethylene oxide and bromination modification has the first after-flame time of 1.8s, the second after-flame time of 1.9s, the second afterglow time of 2.4s and the second total time of 4.4s, and the two test samples have no dripping, are rapidly self-extinguished after being separated from fire, and are judged to be V0 level according to the standard. The flame retardant effect of the modified PPO micro-nano porous material is equivalent to that of a PPO micro-nano porous material which is only modified by bromination. Thus, the flame retardancy of the material is only relevant to the bromination substitution reaction.
Claims (4)
1. The preparation method of the PCB dielectric material for high-frequency and high-speed signal propagation is characterized by comprising the following steps of:
step 1, taking PPO as a raw material, and obtaining a foaming material by a supercritical foaming method;
step 2, carrying out irradiation crosslinking on the foaming material to obtain a crosslinked modified foaming material, wherein the irradiation dose is 10-500 kGy;
step 3, carrying out free radical substitution reaction treatment on the crosslinked modified foaming material obtained in the step 2 to obtain the PPO micro-nano pore foaming material resistant to thermal oxidative aging; the free radical substitution reaction treatment is to carry out substitution reaction with ethylene oxide under the acid or alkaline condition, the reaction temperature is 20-150 ℃, the reaction time is 5 minutes-2 hours, and the hydrogen atoms on the PPO end group and the methyl are replaced;
step 4, performing electrophilic substitution reaction treatment on the benzene ring on the anti-thermal-oxidative aging PPO micro-nano porous foaming material obtained in the step 3 to replace H on the PPO benzene ring; the electrophilic substitution reaction treatment is as follows: and (3) placing the PPO micro-nano porous foaming material with the thermal oxidation aging resistance in a bromine gas environment, wherein the reaction temperature is 20-130 ℃, and the reaction time is 30 minutes-4 hours, so as to obtain the medium material.
2. The method for producing a dielectric material for a PCB for high-frequency and high-speed signal propagation according to claim 1, wherein the dielectric material has a cell pore size of 0.5 to 50 μm and a cell density of 1X 10 6 ～1×10 11 Individual/cm 3 。
3. The method according to claim 1, wherein the supercritical foaming method in step 1 is supercritical CO 2 Is a physical foaming agent, and is processed at 130-200 ℃ and 5-25MPaSwelling the part for 0.1-5 hours, and then decompressing and foaming.
4. Use of the dielectric material obtained by the preparation method of any one of claims 1-3 in a dielectric substrate in a copper-clad laminate of a PCB.
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| JPH09291148A (en) * | 1996-02-29 | 1997-11-11 | Matsushita Electric Works Ltd | Production of modified polyphenylene oxide, epoxy resin composition containing modified polyphenylene oxioe produced by the process, prepreg made using the composition, and laminate made using the prepreg |
| JP2003160726A (en) * | 2001-11-27 | 2003-06-06 | Matsushita Electric Works Ltd | Polyphenylene oxide resin composition, its production method, prepreg, laminated board, printed wiring board and multi-layered printed wiring board |
| CN102890418A (en) * | 2012-09-29 | 2013-01-23 | 京东方科技集团股份有限公司 | Photoresist film formation resin and preparation method thereof |
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| JPH09291148A (en) * | 1996-02-29 | 1997-11-11 | Matsushita Electric Works Ltd | Production of modified polyphenylene oxide, epoxy resin composition containing modified polyphenylene oxioe produced by the process, prepreg made using the composition, and laminate made using the prepreg |
| JP2003160726A (en) * | 2001-11-27 | 2003-06-06 | Matsushita Electric Works Ltd | Polyphenylene oxide resin composition, its production method, prepreg, laminated board, printed wiring board and multi-layered printed wiring board |
| CN102890418A (en) * | 2012-09-29 | 2013-01-23 | 京东方科技集团股份有限公司 | Photoresist film formation resin and preparation method thereof |
| CN112940417A (en) * | 2020-12-28 | 2021-06-11 | 江苏集萃先进高分子材料研究所有限公司 | High-wave-transmittance tetrafluoroethylene copolymer plastic microporous foam material in wide frequency band and green preparation method thereof |
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