CN111909192A - Siloxane with low dielectric constant and loss at high frequency, preparation method and application thereof - Google Patents
Siloxane with low dielectric constant and loss at high frequency, preparation method and application thereof Download PDFInfo
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F130/08—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
Abstract
The invention relates to siloxanes with low dielectric constants and losses at high frequencies, a process for their preparation and their use. Specifically, the invention discloses a siloxane monomer, and a resin obtained by curing the siloxane monomer has low dielectric constant and low dielectric loss, high heat resistance, good processability and low water absorption rate under high frequency, and is particularly suitable for preparing a high-frequency circuit board.
Description
Technical Field
The invention relates to the technical field of high-performance polymers, in particular to siloxane with low dielectric constant and loss at high frequency, and a preparation method and application thereof.
Background
With the rapid development of high frequency communication technology, high frequency low dielectric materials that can be used as matrix resins for high frequency printed circuit boards (HPCBs) are receiving much attention. In order to meet the development requirements of high frequency communication technology, the low dielectric material is used under high frequency condition (>5GHz) should be kept low in dielectric constant (D)k<2.6) and low dielectric losses (D)f<2.0×10-3). In addition, these materials are also required to have good adhesion, high heat resistance, good processability, and low water absorption. Although Polytetrafluoroethylene (PTFE) is commonly used in HPCB manufacture, it has low adhesion to the substrate, is not easily processed, and has low thermal stability due toThere is also a need to develop low dielectric materials with superior overall performance to replace PTFE to meet the application requirements. Industrial resins such as cyanate ester resins, epoxy resins, and benzoxazine resins have been used as matrix resins for printed wiring boards for a long time because of their good substrate adhesion and good processability. However, these resins usually have a curing agent or additive remaining after curing, adversely affect the dielectric constant and loss of the material, and are not so many that the dielectric constant and loss can be kept low under high frequency conditions. Therefore, the development of new high-frequency low-dielectric constant materials is urgently needed to meet the application requirements of the related field.
Disclosure of Invention
The invention aims to provide siloxane (especially fluorine-containing siloxane) with low dielectric constant and loss at high frequency, and a preparation method and application thereof.
In a first aspect of the present invention, a siloxane monomer is provided, the monomer having a structure represented by formula M:
wherein the content of the first and second substances,
each R is independently selected from the group consisting of: hydrogen, halogenated or unsubstituted C1-C15 alkyl, halogenated or unsubstituted C3-C15 cycloalkyl, halogenated or unsubstituted C6-C10 aryl;
Raselected from the group consisting of: substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C6-C10 aryl; wherein, one or more hydrogen atoms on the substituted group are substituted by one or more substituents selected from the group consisting of: halogen, halogenated or unsubstituted C1-C4 alkyl, halogenated or unsubstituted C2-C4 alkenyl, halogenated or unsubstituted C2-C4 alkynyl, halogenated or unsubstituted C1-C4 alkoxy, phenyl;
x is selected from the group consisting of: hydrogen, halogen, halogenated or unsubstituted C1-C6 alkyl, halogenated or unsubstituted C1-C6 alkoxy.
In another preferred embodiment, each R is the same or different, preferably the same.
In another preferred embodiment, each R is independently selected from the group consisting of: halogenated or unsubstituted C1-C12 alkyl, C3-C10 cycloalkyl, phenyl;
Raselected from the group consisting of: phenyl substituted by C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkyl;
x is selected from the group consisting of: halogen, halogenated C1-C6 alkyl, halogenated or unsubstituted C1-C6 alkoxy.
In another preferred embodiment, each R is independently selected from the group consisting of: hydrogen, methyl, ethyl, trifluoropropyl, phenyl, dodecyl.
In another preferred embodiment, RaSelected from the group consisting of: C1-C6 alkyl, C2-C6 alkenyl, substituted or unsubstituted phenyl; wherein, one or more hydrogen atoms on the substituent group are substituted by a substituent selected from the group consisting of: fluorine atom or other halogens, trifluoromethyl, trifluoropropyl, C1-C6 alkoxy, C1-C4 alkyl groups.
In another preferred embodiment, X is selected from the group consisting of: hydrogen, fluorine, trifluoromethyl, trifluoropropyl, C1-C6 alkoxy, C1-C4 alkyl.
In another preferred embodiment, X is selected from the group consisting of: halogen, halogenated C1-C6 alkyl, halogenated C1-C6 alkoxy.
In another preferred embodiment, the monomer is selected from the group consisting of:
in a second aspect of the present invention, there is provided a method for preparing a siloxane monomer according to the first aspect of the present invention, comprising the steps of:
1) reacting a compound of a formula A with a compound of a formula B in a solvent in the presence of a catalyst to obtain a compound of a formula M;
wherein, R, RaAnd X is as defined in the first aspect of the invention;
Rbis a halogenated or unsubstituted C1-C6 alkoxy group.
In another preferred embodiment, step 1) is carried out at 0-80 ℃, preferably 5-40 ℃, more preferably 10-35 ℃.
In another preferred embodiment, the reaction time of step 1) is 0.5 to 12 hours, preferably 1 to 5 hours, more preferably 1.5 to 3 hours.
In another preferred embodiment, the solvent is selected from the group consisting of: tetrahydrofuran, dichloromethane, toluene, or combinations thereof.
In another preferred embodiment, the catalyst is B (C)6F5)3。
In another preferred embodiment, the molar ratio of the compound of formula a to the compound of formula B is 2 to 2.5, preferably 2.
In another preferred embodiment, the molar ratio of the catalyst to the compound of formula B is from 0.003 to 0.1, preferably from 0.005 to 0.05.
In a third aspect of the present invention, there is provided a cured resin obtained by curing the monomer according to the first aspect of the present invention.
In another preferred embodiment, the cured resin has one or more characteristics selected from the group consisting of:
1) the dielectric constant of the cured resin under the condition of 5GHz is less than or equal to 2.9 (preferably less than or equal to 2.8, more preferably less than or equal to 2.7, and most preferably less than or equal to 2.6);
2) the dielectric loss of the cured resin is less than or equal to 3 multiplied by 10 under the condition of 5GHz-3(preferably ≦ 2.5 × 10-3More preferably less than or equal to 2X 10-3)；
3) The glass transition temperature of the cured resin is more than or equal to 200 ℃ (preferably more than or equal to 220 ℃, more preferably more than or equal to 240 ℃);
4) the water absorption of the cured resin is less than or equal to 0.5% (preferably less than or equal to 0.4%, more preferably less than or equal to 0.1%, and most preferably less than or equal to 0.08%).
In a fourth aspect of the present invention, there is provided a method for producing a cured resin according to the third aspect of the present invention, comprising the steps of:
1) the monomer according to the first aspect of the present invention is heated and cured to obtain the cured resin according to the third aspect of the present invention.
In another preferred embodiment, the heat curing is carried out at 80-300 ℃ for 4-10 h.
In another preferred embodiment, the heat curing is performed in steps:
1-1) curing at a first temperature for a first time;
1-2) curing at a second temperature for a second time;
1-3) curing at a third temperature for a third time;
1-4) curing at a fourth temperature for a fourth time to obtain the cured resin.
In another preferred embodiment, the first temperature is 80-120 ℃ and the first time is 0.8-1.5 h.
In another preferred embodiment, the second temperature is 130-180 ℃, and the second time is 0.8-1.5 h.
In another preferred embodiment, the third temperature is 190-230 ℃, and the third time is 1.5-5 h.
In another preferred embodiment, the fourth temperature is 240-300 ℃, and the fourth time is 0.8-1.5 h.
In another preferred embodiment, in step 1), a monomer N selected from the group consisting of: divinyldimethylsilane, tetramethyldivinyldisiloxane, tetramethyltetravinylcyclotetrasiloxane, trivinyltrimethylcyclotrisiloxane, or a combination thereof.
In another preferred embodiment, the monomer N and the monomer of the first aspect of the present invention are preformed by a forming process selected from the group consisting of: pouring a mold, spin-coating the solution, and dripping the solution.
In another preferred embodiment, the solution spin coating or solution drop coating comprises the steps of: dissolving the monomer of the first aspect of the invention alone or together with the monomer N in an organic solvent to prepare a solution, and then carrying out spin coating or drop coating; the solvent is selected from the following group: toluene, xylene, trimethylbenzene, diphenyl ether, cyclohexanone, chloroform, acetone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, or a combination thereof.
In a fifth aspect of the present invention, there is provided a use of the cured resin according to the third aspect of the present invention for producing a high frequency printed circuit board.
In a sixth aspect of the present invention, there is provided a high-frequency printed wiring board, wherein a base resin for preparing the high-frequency printed wiring board is obtained by curing the siloxane monomer according to the first aspect of the present invention or a mixture containing the siloxane monomer according to the first aspect of the present invention.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Detailed Description
The inventor of the invention has conducted long-term and intensive research and obtains the fluorine-containing siloxane with low dielectric constant and loss at high frequency by optimizing the preparation process, and the preparation method and the application thereof. On this basis, the inventors have completed the present invention.
Term(s) for
In the present invention, unless otherwise specified, the terms used have the ordinary meanings well known to those skilled in the art.
In the present invention, the term "halogen" means F, Cl, Br or I.
In the present invention, "C1-C15 alkyl" means a straight or branched chain alkyl group including 1 to 15 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, tert-pentyl, or the like. "C1-C12 alkyl", "C1-C6 alkyl" and "C1-C4 alkyl" have similar meanings.
In the present invention, the term "C2-C6 alkenyl group" means a straight or branched chain alkenyl group having 2 to 6 carbon atoms containing one double bond, including, but not limited to, ethenyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl and the like. "C2-C4 alkenyl" has similar meaning.
In the present invention, the term "C2-C4 alkynyl" refers to a straight or branched alkynyl group having 2 to 4 carbon atoms containing one triple bond, including, but not limited to, ethynyl, propynyl, butynyl, isobutynyl, and the like.
In the present invention, the term "C3-C15 cycloalkyl" refers to a cyclic alkyl group having 3 to 15 carbon atoms in the ring, including, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. "C3-C10 cycloalkyl", "C3-C8 cycloalkyl" and "C3-C6 cycloalkyl" have similar meanings.
In the present invention, the term "C1-C6 alkoxy" means a straight or branched chain alkoxy group having 1 to 6 carbon atoms, including, but not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy and the like. C1-C4 alkoxy is preferred.
In the present invention, the term "aromatic ring" or "aryl" has the same meaning, and is preferably "C6-C10 aryl". The term "C6-C10 aryl" refers to an aromatic ring group having 6-10 carbon atoms, such as phenyl, naphthyl, and the like, which does not contain heteroatoms in the ring.
In the present invention, the term "halo" means substituted by halogen.
In the present invention, the term "substituted" means that one or more hydrogen atoms on a specified group are replaced with a specified substituent. Particular substituents are those described correspondingly in the foregoing, or as appearing in the examples. Unless otherwise specified, a certain substituted group may have one substituent selected from a specific group at any substitutable site of the group, and the substituents may be the same or different at each position. It will be understood by those skilled in the art that the combinations of substituents contemplated by the present invention are those that are stable or chemically achievable. Such substituents are for example (but not limited to): halogen, hydroxyl, carboxyl (-COOH), C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, 3-to 12-membered heterocyclyl, aryl, heteroaryl, C1-C8 aldehyde, C2-C10 acyl, C2-C10 ester, amino, C1-C6 alkoxy, C1-C10 sulfonyl and the like.
In the present invention, the terms 1 to 6 mean 1, 2, 3, 4, 5 or 6. Other similar terms have similar meanings.
The term "plurality" means 1, 2, 3, 4, 5 or 6.
(fluorine-containing) siloxane and preparation method thereof
It has been found that polysiloxanes generally have a higher dielectric constant, but they have good processability and higher thermal stability. Further research shows that the fluorine group and the bulky group exist in the polymer simultaneously, so that the dielectric constant and the dielectric loss of the material can be effectively reduced. For example, by introducing a perfluorocyclobutane group as a main chain or a side chain into polysiloxane, the dielectric constant and dielectric loss (D) of the polymer can be effectively reducedk<2.6 and Df<4.0×10-3). However, the polymer containing perfluorocyclobutane group has low yield and high synthesis difficulty because the monomer is prepared through multi-step reaction. As a result of further studies, the present inventors have provided a simpler method for synthesizing a fluorine-containing organosiloxane resin.
The invention designs and synthesizes a novel fluorine-containing siloxane monomer with a styrene crosslinking group. In consideration of the availability of raw materials and the convenience of a synthesis method, the fluorine-containing aryl halogenated hydrocarbon is synthesized by adopting a milder reaction. The obtained resin shows low dielectric constant and dielectric loss at a high frequency of 5GHz after curing, and has low water absorption and good heat resistance. The fluorine-containing polysiloxane resin prepared by the invention can provide novel matrix resin for preparing high-frequency printed circuit boards for the field of high-frequency communication.
The invention relates to a fluorine-containing siloxane resin with low dielectric constant and low dielectric loss under the condition of high frequency (more than 5GHz) and a preparation method thereof. Specifically, the raw material is fluorine-containing ethoxy siloxane and silane containing styryl crosslinking group, and a small amount of B (C)6F5)3In toluene in the presence of a catalystAnd synthesizing the crosslinkable fluorine-containing siloxane monomer by a Piers-Rubinsztajn reaction one-pot method. After the monomer is cured, fluorine-containing polysiloxane with excellent dielectric constant and dielectric loss at high frequency of more than 5GHz is obtained. The crosslinkable fluorine-containing siloxane monomer provided by the invention has good processing performance, and the resin formed after the monomer is cured has excellent heat resistance and low water absorption, and shows low dielectric constant and dielectric loss under high frequency. The synthesis method provided by the invention has the advantages of easily available raw materials, mild reaction conditions and high yield, and the obtained fluorine-containing crosslinkable siloxane can be used as a low dielectric constant material and is used in the fields of high-frequency communication, aerospace, national defense and the like.
The compound of formula B according to the present invention is prepared by conventional methods or as follows:
under the protection of inert gas, adding magnesium chips or magnesium strips, anhydrous tetrahydrofuran or diethyl ether, iodine and silane into a reaction device
Dropwise adding 4-halogenated fluorobenzene or 4-bromoanisole, and reacting at 0-80 ℃ for 3-30 hours to obtain a compound shown in the formula B;
wherein the 4-halogenated fluorobenzene is 4-iodo fluorobenzene, 4-bromo fluorobenzene and 4-chloro fluorobenzene; wherein X is selected from the group consisting of: fluorine atom, trifluoromethyl, trifluoropropyl, C1-C4 alkoxy, C1-C4 alkyl.
The magnesium chips or magnesium strips, anhydrous tetrahydrofuran or diethyl ether, iodine,
And 4-halogenated fluorobenzene or 4-bromoanisole in a molar ratio of 1-1.5:1-12:0.0005-0.01:1-5: 1.
Compared with the prior art, the invention has the following main advantages:
(1) the invention relates to a method for synthesizing fluorine-containing siloxane. The invention synthesizes the monomer with the crosslinking group based on the one-pot method, has mild reaction conditions in the synthesis steps, simple preparation process and high yield, and can be used for industrial large-scale production.
(2) The invention synthesizes a series of polysiloxane resins with novel chemical structures. The monomer is directly thermally cured to obtain the polysiloxane resin, and the designed polysiloxane resin has good processing performance.
(3) The fluorosilicone obtained by the invention shows higher heat resistance and lower water absorption after being cured (<0.18%) and exhibits good dielectric properties under high frequency conditions of 5GHz (dielectric constant as low as 2.53, dielectric loss of 1.66X 10)-3). Is a novel high-temperature curing fluorine-containing organic silicon resin, and can be used as a high-performance resin matrix or a packaging material for the fields of high-frequency communication, large-scale integrated circuits, microelectronic industry, aerospace and the like.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
Universal test method
DMA test (i.e. dynamic thermomechanical analysis)
Dynamic thermomechanical analysis (DMA) was tested by a DMA/SDTA861e instrument under a nitrogen atmosphere with a heating rate of 3 deg.C/min.
Dielectric property test
The dielectric constant and dielectric loss were measured by a split dielectric resonator (QWED) at room temperature at a frequency of 5 GHz.
Water absorption test
The cured resin sheet was dried under vacuum at 100 ℃ until the weight was constant, and then soaked in boiling water for several days. The water absorption was calculated from the increase in weight of the cured resin sheet after soaking.
EXAMPLE 1 Synthesis of methoxy group-containing siloxane monomer M1
A100 mL round-bottomed flask was charged with 20mmol of Compound 2a and 0.1mmol of B (C)6F5)310mL of toluene, 40mmol of dimethylsilylene hydrosilane 1 dissolved in 10mL of toluene was added dropwise with stirring. After the addition was complete, the mixture was stirred vigorously at room temperature for 2 hours. The solvent was removed under reduced pressure, and column chromatography was carried out to give methoxysiloxane-containing monomer M1 as a colorless transparent liquid in 73% yield.
1H NMR(CDCl3,400MHz),(ppm)7.57～7.39(m,6H),7.34(d,J＝8.0Hz,4H),7.01～6.78(m,2H),6.70(dd,J＝17.6,10.9Hz,2H),5.77(dd,J＝17.6,0.8Hz,2H),5.25(dd,J＝10.9,0.8Hz,2H),3.78(s,3H),0.31(d,J＝2.5Hz,12H),0.28(s,3H).
13C NMR(CDCl3,101MHz),(ppm)160.77,139.12,138.33,136.88,134.81,133.33,129.09,125.47,114.18,113.33,54.93,0.76,0.15.
Wherein reactant 2a is prepared according to conventional methods. Under the protection of nitrogen gas, a 250mL dry three-neck flask is added with a magneton and stirred, 60mmol magnesium chips, 100mL tetrahydrofuran, 60mmol methyl triethoxysilane and one iodine, then 50mmol 4-bromoanisole is added, and the mixture is stirred and reacted for 12 hours at room temperature. After removing the solvent under reduced pressure, n-hexane was added to dissolve again, and a precipitate was precipitated. Filtration through celite gave a filtrate which was concentrated and pure 2a was obtained by distillation under reduced pressure in 66% yield.
1H NMR(CDCl3,400MHz),(ppm)7.58(d,J＝8.3Hz,2H),6.92(d,J＝8.3Hz,2H),3.82～3.76(m,4H),3.79(s,3H),1.23(t,J＝7.2Hz,6H),0.33(s,3H).
13C NMR(CDCl3,126MHz),(ppm)161.02,135.49,125.75,113.44,58.30,54.81,18.23,-4.17.
Example 2 Synthesis of Fluorosiloxane monomer M2
The experimental procedure was the same as in example 1, and column chromatography was carried out to give the target fluorosilicone monomer M2 in 77% yield.
1H NMR(CDCl3,400MHz),(ppm)7.58～7.43(m,6H),7.40～7.26(m,4H),7.01～7.00(m,2H),6.69(dd,J＝17.6,10.9Hz,2H),5.77(dd,J＝17.6,1.0Hz,2H),5.25(dd,J＝10.9,1.0Hz,2H),0.32(d,J＝2.8Hz,12H),0.29(s,3H).
13C NMR(CDCl3,101MHz),(ppm)164.97(d,J＝248.9Hz),138.81,138.46,136.83,135.31(d,J＝7.4Hz),133.55(d,J＝3.9Hz),133.30,125.53,114.86(d,J＝19.8Hz),114.29,0.69,0.04.
Reactant 2b was prepared as in example 1, except that: using 4-fluorobromobenzene instead of 4-bromoanisole, 2b was purified by distillation in 62% yield.
1H NMR(CDCl3,400MHz),(ppm)7.64～7.60(m,2H),7.10～7.04(m,2H),3.86～3.75(m,4H),1.25(t,J＝6.8Hz,6H),0.35(s,3H).19F NMR(CDCl3,376MHz),(ppm)-110.3.
13C NMR(CDCl3,126MHz),(ppm)165.18(d,J＝249.5Hz,136.04(d,J＝7.6Hz),130.49(d,J＝3.5Hz),114.95(d,J＝19.7Hz),58.38,18.16,-4.32.
Example 3 Synthesis of Trifluoromethylsiloxane monomer M3
The experimental procedure was substantially the same as in example 1, and column chromatography was carried out to obtain the target fluorosilicone monomer M3 in a yield of 79%.
1H NMR(CDCl3,400MHz),(ppm)7.59(d,J＝7.8Hz,2H),7.54(d,J＝7.8Hz,2H),7.45(d,J＝7.6Hz,4H),7.35(d,J＝7.6Hz,4H),6.71(dd,J＝17.6,10.9Hz,2H),5.78(d,J＝17.6Hz,2H),5.27(d,J＝10.9Hz,2H),0.37～0.26(m,15H).
19F NMR(CDCl3,376MHz),(ppm)-62.81.13C NMR(CDCl3,126MHz),(ppm)142.42,138.55,136.78,136.78,133.49,133.26,131.77(q,J＝32.1Hz),127.43(q,J＝272.7Hz),125.55,124.23(q,J＝3.7Hz),114.39,0.63,-0.15.
Reactant 2c was prepared as in example 1, except that: pure 2c was obtained by distillation under reduced pressure using 4-bromotrifluorotoluene instead of 4-bromoanisole in a yield of 45%.
1H NMR(CDCl3,400MHz),(ppm)7.77(d,J＝7.6Hz,2H),7.62(d,J＝7.6Hz,2H),3.87～3.80(m,4H),1.25(t,J＝7.1Hz,6H),0.37(s,3H).
19F NMR(CDCl3,376MHz),(ppm)-63.05.
13C NMR(CDCl3,126MHz),(ppm)139.75,134.34(q,J＝32.4Hz),132.20,127.42(q,J＝272.7Hz),124.37(q,J＝3.9Hz),58.65,18.22,-4.38.
Example 4 Synthesis of Trifluoromethylsiloxane-containing monomer M4
Column chromatography gave the target fluorosilicone monomer M4 in 83% yield.
1H NMR(CDCl3,400MHz),(ppm)7.60(d,J＝7.9Hz,4H),7.55(d,J＝7.9Hz,4H),7.42(d,J＝8.0Hz,4H),7.33(d,J＝8.0Hz,4H),6.70(dd,J＝17.6,10.9Hz,2H),5.78(dd,J＝17.6,0.9Hz,2H),5.27(dd,J＝10.9,0.9Hz,2H),0.34(s,12H).
19F NMR(CDCl3,376MHz),(ppm)-62.84.
13C NMR(CDCl3,126MHz),(ppm)139.79,138.80,137.85,136.71,134.43,133.28,132.38(q,J＝32.4Hz),127.35(q,J＝272.8Hz),125.64,124.46(q,J＝3.8Hz),114.56,0.51.
The synthesis of reactant 2d is the same as example 1, except that: pure 2d was obtained by distillation under reduced pressure using 4-bromotrifluorotoluene (90mmol) instead of 50mmol of 4-bromoanisole and tetraethoxysilane (45mmol) instead of methyltriethoxysilane (60mmol) in 60% yield.
1H NMR(CDCl3,400MHz),(ppm)7.81(d,J＝7.6Hz,4H),7.63(d,J＝7.6Hz,4H),3.90(q,J＝6.8Hz,4H),1.28(t,J＝6.8Hz,6H).19F NMR(CDCl3,376MHz),(ppm)-63.20.
13C NMR(CDCl3,126MHz)(ppm)137.51,135.24,132.83(q,J＝32.4Hz),127.45(q,J＝272.5Hz),124.61(q,J＝3.9Hz),59.33,18.16.
EXAMPLE 5 curing and Properties of methoxy-containing Silicone resin M1
The target methoxy group-containing siloxane monomer M1 prepared in example 1 was placed in a tube furnace and cured at 100 ℃ for 1 hour, 150 ℃ for 1 hour, 200 ℃ for 3 hours and 250 ℃ for 1 hour to give a cured resin M1. The glass transition temperature was measured to be 234 ℃ using DMA. The cured sample was polished into a wafer (thickness 1.983mm, diameter 3.2cm), and the dielectric properties were measured, which revealed that the dielectric constant at 5GHz was 2.78 and the dielectric loss was 2.07X 10-2. After soaking in boiling water for 96h, the water absorption was tested to be 0.38%. The dielectric property of the soaked sample is measured again, and the result shows that the dielectric constant is 2.78 and the dielectric loss is 2.38 multiplied by 10 under the condition of 5GHz-2。
EXAMPLE 6 curing and Properties of Fluorosiloxane resin M2
The target fluorosilicone monomer M2 prepared in example 2 was placed in a tube furnace, and cured at 100 ℃ for 1 hour, 150 ℃ for 1 hour, 200 ℃ for 3 hours and 250 ℃ for 1 hour to give a cured resin M2. The glass transition temperature was 255 ℃ by DMA test. The cured sample was polished into a round piece (thickness 0.958mm, diameter 3.2cm), and the dielectric properties were measured, whereby the dielectric constant at 5GHz was 2.64 and the dielectric loss was 2.00X 10-3. In boiling waterAfter soaking for 96h, the water absorption rate is tested to be 0.18%. The dielectric property of the soaked sample is measured again, and the result shows that the dielectric constant is 2.67 and the dielectric loss is 2.13 multiplied by 10 under the condition of 5GHz-3。
Example 7 curing and Properties of Trifluoromethylsiloxane-containing resin M3
The target trifluoromethylsiloxane-containing monomer M3 prepared in example 3 was placed in a tube furnace, and cured at 100 ℃ for 1 hour, 150 ℃ for 1 hour, 200 ℃ for 3 hours and 250 ℃ for 1 hour to give a cured resin M3. The glass transition temperature was 218 ℃ as measured by DMA. The cured sample was polished into a round piece (thickness 1.763mm, diameter 3.2cm), and the dielectric properties were measured, which revealed that the dielectric constant at 5GHz was 2.56 and the dielectric loss was 2.41X 10-3. After soaking in boiling water for 96h, the water absorption was tested to be 0.091%. The dielectric property of the soaked sample is measured again, and the result shows that the dielectric constant is 2.57 and the dielectric loss is 2.42 multiplied by 10 under the condition of 5GHz-3。
EXAMPLE 8 curing and Properties of Trifluoromethylsiloxane-containing resin M4
The target trifluoromethylsiloxane-containing monomer M4 prepared in example 4 was placed in a tube furnace, and cured at 100 ℃ for 1 hour, 150 ℃ for 1 hour, 200 ℃ for 3 hours and 250 ℃ for 1 hour to give a cured resin M4. The glass transition temperature was 249 ℃ by DMA test. The cured sample was polished into a round piece (thickness 1.701mm, diameter 3.2cm), and the dielectric properties were measured, which revealed that the dielectric constant at 5GHz was 2.53 and the dielectric loss was 1.66X 10-3. After soaking in boiling water for 96h, the water absorption was tested to be 0.061%. The dielectric property of the soaked sample is measured again, and the result shows that the dielectric constant is 2.57 and the dielectric loss is 1.82 multiplied by 10 under the condition of 5GHz-3。
The performance data for examples 5-8 are summarized in Table 1.
TABLE 1
As can be seen from the above examples, the fluorosilicone resin (cured resin M4) had a lower dielectric constant and lower dielectric loss than the methoxy group-containing polysiloxane resin (cured resin M1). And the fluorine-containing siloxane resin has low water absorption rate, and can still keep low dielectric constant and dielectric loss after being soaked in boiling water for 96 h. The fluorine-containing siloxane resin synthesized by the method has excellent performance, and can be used as matrix resin for preparing high-frequency circuit boards.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (10)
1. A siloxane monomer having a structure according to formula M:
wherein the content of the first and second substances,
each R is independently selected from the group consisting of: hydrogen, halogenated or unsubstituted C1-C15 alkyl, halogenated or unsubstituted C3-C15 cycloalkyl, halogenated or unsubstituted C6-C10 aryl;
Raselected from the group consisting of: substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C6-C10 aryl; wherein, one or more hydrogen atoms on the substituted group are substituted by one or more substituents selected from the group consisting of: halogen, halogenated or unsubstituted C1-C4 alkyl, halogenated or unsubstituted C2-C4 alkenyl, halogenated or unsubstituted C2-C4 alkynyl, halogenated or unsubstituted C1-C4 alkoxy, phenyl;
x is selected from the group consisting of: hydrogen, halogen, halogenated or unsubstituted C1-C6 alkyl, halogenated or unsubstituted C1-C6 alkoxy.
2. The monomer of claim 1,
each R is independently selected from the group consisting of: halogenated or unsubstituted C1-C12 alkyl, C3-C10 cycloalkyl, phenyl;
Raselected from the group consisting of: phenyl substituted by C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkyl;
x is selected from the group consisting of: halogen, halogenated C1-C6 alkyl, halogenated or unsubstituted C1-C6 alkoxy.
3. The monomer of claim 1, wherein X is selected from the group consisting of: halogen, halogenated C1-C6 alkyl, halogenated C1-C6 alkoxy.
4. The monomer of claim 1, wherein the monomer is selected from the group consisting of:
5. a method of preparing the siloxane monomer of claim 1, comprising the steps of:
1) reacting a compound of a formula A with a compound of a formula B in a solvent in the presence of a catalyst to obtain a compound of a formula M;
wherein, R, RaAnd X is as defined in claim 1;
Rbis a halogenated or unsubstituted C1-C6 alkoxy group.
6. The method of claim 5, wherein the catalyst is B (C)6F5)3。
7. A cured resin obtained by curing the monomer according to claim 1.
8. A method for preparing the cured resin according to claim 7, comprising the steps of:
1) heating and curing the monomer of claim 1 to obtain the cured resin of claim 7.
9. Use of the cured resin according to claim 7 for the production of high frequency printed circuit boards.
10. A high-frequency printed wiring board characterized in that a base resin for producing the high-frequency printed wiring board is obtained by curing the siloxane monomer according to claim 1 or a mixture containing the siloxane monomer according to claim 1.
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| CN111909192B (en) * | 2020-08-13 | 2022-06-21 | 中国科学院上海有机化学研究所 | Siloxane with low dielectric constant and loss at high frequency, preparation method and application thereof |
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