WO2022033255A1 - 高频下具有低介电常数和损耗的硅氧烷及其制备方法和应用 - Google Patents

高频下具有低介电常数和损耗的硅氧烷及其制备方法和应用 Download PDF

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WO2022033255A1
WO2022033255A1 PCT/CN2021/105557 CN2021105557W WO2022033255A1 WO 2022033255 A1 WO2022033255 A1 WO 2022033255A1 CN 2021105557 W CN2021105557 W CN 2021105557W WO 2022033255 A1 WO2022033255 A1 WO 2022033255A1
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unsubstituted
halogenated
group
monomer
alkyl
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房强
刘凤萍
孙晶
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中国科学院上海有机化学研究所
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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 Table
    • 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
    • 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 Table
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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

Definitions

  • the present invention relates to the technical field of high-performance polymers, in particular to a siloxane with low dielectric constant and loss at high frequency, and a preparation method and application thereof.
  • high-frequency and low-dielectric materials that can be used as matrix resins for high-frequency printed circuit boards (HPCB) have received extensive attention.
  • low dielectric materials should maintain low dielectric constant (D k ⁇ 2.6) and low dielectric loss (D f ⁇ 2.0 ⁇ 10 -3 ) under high frequency conditions (>5GHz).
  • these materials are required to have good adhesion, high heat resistance, good processability and low water absorption.
  • polytetrafluoroethylene (PTFE) is commonly used in HPCB manufacturing, it has low adhesion to substrates, is not easy to process and has low thermal stability.
  • the purpose of the present invention is to provide a siloxane (especially fluorine-containing siloxane) with low dielectric constant and loss at high frequency and its preparation method and application.
  • the first aspect of the present invention provides a siloxane monomer, the monomer has the structure shown in formula M:
  • 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;
  • R a is selected 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 alkane Oxygen, substituted or unsubstituted C6-C10 aryl; wherein, the substitution refers to the substitution of one or more hydrogen atoms on the group by one or more substituents selected from the group consisting of halogen, halogenated or unsubstituted Substituted 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.
  • each R is the same or different, preferably the same.
  • each R is independently selected from the following group: halogenated or unsubstituted C1-C12 alkyl, C3-C10 cycloalkyl, phenyl;
  • R a is selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkyl substituted phenyl;
  • X is selected from the group consisting of halogen, halogenated C1-C6 alkyl, halogenated or unsubstituted C1-C6 alkoxy.
  • each R is independently selected from the group consisting of hydrogen, methyl, ethyl, trifluoropropyl, phenyl, and dodecyl.
  • R a is selected from the following group: C1-C6 alkyl, C2-C6 alkenyl, substituted or unsubstituted phenyl; wherein, the substitution refers to one or more hydrogen atoms on the group Substituted with a substituent selected from the group consisting of a fluorine atom or other halogen, trifluoromethyl, trifluoropropyl, C1-C6 alkoxy, C1-C4 alkyl.
  • X is selected from the group consisting of hydrogen, fluorine, trifluoromethyl, trifluoropropyl, C1-C6 alkoxy, and C1-C4 alkyl.
  • X is selected from the group consisting of halogen, halogenated C1-C6 alkyl, and halogenated C1-C6 alkoxy.
  • the monomer is selected from the following group:
  • the second aspect of the present invention provides a preparation method of the siloxane monomer described in the first aspect of the present invention, comprising the following steps:
  • R, Ra and X are as defined in the first aspect of the present invention.
  • R b is halogenated or unsubstituted C1-C6 alkoxy.
  • step 1) is carried out at 0-80°C, preferably 5-40°C, more preferably 10-35°C.
  • reaction time of step 1) is 0.5-12h, preferably 1-5h, more preferably 1.5-3h.
  • the solvent is selected from the group consisting of tetrahydrofuran, dichloromethane, toluene, or a combination thereof.
  • the catalyst is B(C 6 F 5 ) 3 .
  • the molar ratio of the compound of formula A to the compound of formula B is 2-2.5, preferably 2.
  • the molar ratio of the catalyst to the compound of formula B is 0.003-0.1, preferably 0.005-0.05.
  • a third aspect of the present invention provides a cured resin obtained by curing the monomer described in the first aspect of the present invention.
  • the cured resin has one or more features selected from the group consisting of:
  • the glass transition temperature of the cured resin is ⁇ 200°C (preferably ⁇ 220°C, more preferably ⁇ 240°C);
  • the water absorption of the cured resin is ⁇ 0.5% (preferably ⁇ 0.4%, more preferably ⁇ 0.1%, most preferably ⁇ 0.08%).
  • the fourth aspect of the present invention provides a preparation method of the cured resin described in the third aspect of the present invention, comprising the following steps:
  • the heat curing is performed at 80-300° C. for 4-10 hours.
  • heating and curing is carried out in steps:
  • the first temperature is 80-120° C.
  • the first time is 0.8-1.5 h.
  • the second temperature is 130-180° C.
  • the second time is 0.8-1.5 h.
  • the third temperature is 190-230° C., and the third time is 1.5-5 h.
  • the fourth temperature is 240-300° C.
  • the fourth time is 0.8-1.5 h.
  • step 1) a monomer N selected from the group of Vinyldisiloxane, tetramethyltetravinylcyclotetrasiloxane, trivinyltrimethylcyclotrisiloxane, or a combination thereof.
  • the monomer N and the monomer described in the first aspect of the present invention are pre-formed by a molding process selected from the following group, and then heated and cured: mold filling, solution spin coating, and solution drop coating.
  • the solution spin coating or solution drop coating comprises the steps of: dissolving the monomer described in the first aspect of the present invention alone or with the monomer N in an organic solvent to prepare a solution, and then spin coating or drop coating coating;
  • the solvent is selected from the following group: toluene, xylene, trimethylbenzene, diphenyl ether, cyclohexanone, chloroform, acetone, N,N-dimethylformamide, N,N-dimethylformamide Acetamide, dimethyl sulfoxide, N-methylpyrrolidone, triglyme, tetraglyme, or combinations thereof.
  • a fifth aspect of the present invention provides a use of the cured resin described in the third aspect of the present invention for preparing a high-frequency printed circuit board.
  • the sixth aspect of the present invention provides a high-frequency printed circuit board, and the matrix resin used for preparing the high-frequency printed circuit board is composed of the siloxane monomer described in the first aspect of the present invention or containing the siloxane monomer of the first aspect of the present invention.
  • the mixture of siloxane monomers is cured.
  • the inventors After long-term and in-depth research, the inventors have obtained a fluorine-containing siloxane with low dielectric constant and loss at high frequency by optimizing the preparation process, and a preparation method and application thereof. On this basis, the inventors have completed the present invention.
  • halogen refers to F, Cl, Br or I.
  • C1-C15 alkyl refers to a straight-chain or branched alkyl group including 1-15 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl , tert-butyl, neopentyl, p-pentyl, or similar groups.
  • C1-C12 alkyl “C1-C6 alkyl” and “C1-C4 alkyl” have similar meanings.
  • C2-C6 alkenyl refers to a straight-chain or branched alkenyl group with 2-6 carbon atoms containing one double bond, including non-limiting vinyl, propenyl, butenyl , isobutenyl, pentenyl and hexenyl, etc.
  • C2-C4 alkenyl has a similar meaning.
  • C2-C4alkynyl refers to a straight or branched chain alkynyl group having 2-4 carbon atoms and containing one triple bond, including, without limitation, ethynyl, propynyl, butyne base, isobutynyl, etc.
  • C3-C15 cycloalkyl refers to a cyclic alkyl group having 3-15 carbon atoms in the ring, including, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclo Hexyl, cycloheptyl, cyclooctyl, etc.
  • C3-C10 cycloalkyl “C3-C8 cycloalkyl” and “C3-C6 cycloalkyl” have similar meanings.
  • C1-C6 alkoxy refers to a straight-chain or branched alkoxy having 1-6 carbon atoms, including, without limitation, methoxy, ethoxy, propoxy, isopropoxy and butoxy, etc. Preferred is C1-C4 alkoxy.
  • aromatic ring or "aryl group” has the same meaning, preferably “C6-C10 aryl group”.
  • 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.
  • halo refers to substitution with halogen.
  • substituted refers to the replacement of one or more hydrogen atoms on a specified group with a specified substituent.
  • substituents are those described correspondingly in the preceding paragraphs, or the substituents appearing in the various examples.
  • a substituted group may have at any substitutable position of the group a substituent selected from a particular group, which may be the same or different at each position. It will be understood by those skilled in the art that combinations of substituents contemplated by the present invention are those that are stable or chemically achievable.
  • the 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 heterocyclic group, aryl group, heteroaryl group, C1-C8 aldehyde group, C2-C10 acyl group, C2-C10 ester group, amino group, C1-C6 alkoxy group, C1-C10 sulfonyl group, etc.
  • the terms 1-6 refer to 1, 2, 3, 4, 5 or 6. Other similar terms have similar meanings.
  • polysiloxanes generally have high dielectric constants, but they have good processability and high thermal stability. Further research shows that the coexistence of fluorine groups and bulky groups in polymers can effectively reduce the dielectric constant and dielectric loss of materials. For example, the dielectric constant and dielectric loss (D k ⁇ 2.6 and D f ⁇ 4.0 ⁇ 10) of polymers can be effectively reduced by introducing perfluorocyclobutane groups as main or side chains in polysiloxanes -3 ). However, polymers containing perfluorocyclobutane groups have low yields and are difficult to synthesize due to the fact that the monomers need to undergo multi-step reactions to obtain them. After further research, the present inventor provides a relatively simple method for synthesizing fluorine-containing organosiloxane resin.
  • the invention designs and synthesizes a new type of fluorine-containing siloxane monomer with styrene cross-linking group. Considering the availability of raw materials and the convenience of synthetic methods, we start from fluorine-containing aryl halogenated hydrocarbons and adopt a milder reaction for synthesis. The obtained resin exhibits low dielectric constant and dielectric loss at a high frequency of 5 GHz after curing, and has low water absorption and good heat resistance.
  • the fluorine-containing polysiloxane resin prepared by the invention can provide a novel matrix resin for preparing high-frequency printed circuit boards in 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 (greater than 5G Hz) and a preparation method thereof.
  • a fluorine-containing siloxane resin with low dielectric constant and low dielectric loss under the condition of high frequency (greater than 5G Hz) and a preparation method thereof.
  • fluorine-containing ethoxysiloxane and styryl cross-linking group-containing silanol as raw materials, in the presence of a small amount of B(C 6 F 5 ) 3 catalyst, in toluene.
  • One-pot synthesis of crosslinkable fluorosiloxane monomers via Piers-Rubinsztajn reaction After the monomer is cured, a fluorine-containing polysiloxane with excellent dielectric constant and dielectric loss is obtained at a high frequency greater than 5G Hz.
  • the crosslinkable fluorine-containing siloxane monomer proposed by the present invention has good processability, and the resin formed after curing of the monomer has excellent heat resistance and low water absorption, and exhibits low dielectric properties at high frequencies Constant and Dielectric Loss.
  • the synthesis method provided by the invention has 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 for high-frequency communication, aerospace, national defense, etc. field.
  • the compound of formula B of the present invention is prepared by conventional methods or as follows:
  • the 4-halogenated fluorine-containing benzene is 4-iodine-substituted fluorine-containing benzene, 4-bromo-fluorinated benzene and 4-chloro-fluorinated benzene; wherein X is selected from the following group: fluorine atom, trifluoromethane base, trifluoropropyl, C1-C4 alkoxy, C1-C4 alkyl.
  • the present invention has the following main advantages:
  • the present invention relates to a method for synthesizing fluorine-containing siloxane.
  • the invention is based on one-pot synthesis of monomers with cross-linking groups, the synthesis step has mild reaction conditions, simple preparation process and high yield, and can be used for industrialized large-scale production.
  • the present invention has synthesized a series of polysiloxane resins with novel chemical structures.
  • the monomer is directly thermally cured to obtain a polysiloxane resin, and the designed polysiloxane resin has good processability.
  • the fluorine-containing siloxane obtained in the present invention exhibits high heat resistance and low water absorption ( ⁇ 0.18%) after curing, and exhibits good dielectric properties (dielectric The constant is as low as 2.53 and the dielectric loss is 1.66 ⁇ 10 -3 ). It is a new type of high-temperature curing fluorine-containing silicone resin, which can be used as a high-performance resin matrix or packaging material for high-frequency communication, large-scale integrated circuits, microelectronics industry, aerospace and other fields.
  • DMA Dynamic thermomechanical analysis
  • the dielectric constant and dielectric loss were measured by a split dielectric resonator (QWED) at room temperature at a frequency of 5 GHz.
  • QWED split dielectric resonator
  • the cured resin sheet was dried under vacuum at 100°C to a constant weight, and then soaked in boiling water for several days.
  • the water absorption rate of the cured resin sheet was calculated based on the increase in weight after soaking.
  • reactant 2a is prepared by conventional method. Under the protection of nitrogen gas, magnetic stirring, 60 mmol magnesium turnings, 100 mL tetrahydrofuran, 60 mmol methyltriethoxysilane and a grain of iodine were added to a 250 mL dry three-necked flask, then 50 mmol 4-bromoanisole was added, and stirring at room temperature The reaction was carried out for 12 hours. After the solvent was removed under reduced pressure, n-hexane was added to dissolve again, and a precipitate was deposited. The filtrate was obtained by filtration through celite, concentrated, and pure 2a was obtained by distillation under reduced pressure in a yield of 66%.
  • the experimental method is the same as that of Example 1.
  • the target fluorine-containing siloxane monomer M2 is obtained by column chromatography, and the yield is 77%.
  • reactant 2b is the same as that of Example 1, except that 4-fluorobromobenzene is used instead of 4-bromoanisole, 2b is purified by distillation, and the yield is 62%.
  • the experimental method is basically the same as that of Example 1.
  • the target fluorine-containing siloxane monomer M3 is obtained by column chromatography, and the yield is 79%.
  • the preparation method of reactant 2c is the same as that in Example 1, except that 4-bromotrifluorotoluene is used instead of 4-bromoanisole, and pure 2c is obtained by distillation under reduced pressure, and the yield is 45%.
  • the target fluorine-containing siloxane monomer M4 was obtained by column chromatography with a yield of 83%.
  • the synthetic method of reactant 2d is the same as in Example 1, except that 4-bromotrifluorotoluene (90mmol) is used to replace 50mmol 4-bromoanisole, and tetraethoxysilane (45mmol) is used to replace methyltriethoxysilane. (60mmol), pure 2d was obtained by distillation under reduced pressure, and the yield was 60%.
  • the target methoxysiloxane-containing monomer M1 prepared in Example 1 was placed in a tube furnace, heated to 100 °C for 1 hour, 150 °C for 1 hour, 200 °C for 3 hours and 250 °C for 1 hour to obtain a cured resin M1. Its glass transition temperature was 234°C measured by DMA.
  • the cured sample was ground into a disc (thickness 1.983mm, diameter 3.2cm), and its dielectric properties were measured. The results showed that the dielectric constant was 2.78 and the dielectric loss was 2.07 ⁇ 10 -2 at 5GHz. After soaking in boiling water for 96 hours, the water absorption rate was 0.38%. The dielectric properties of the soaked samples were measured again, and the results showed that the dielectric constant was 2.78 and the dielectric loss was 2.38 ⁇ 10 -2 under the condition of 5GHz.
  • the target fluorine-containing siloxane monomer M2 prepared in Example 2 was placed in a tube furnace, heated to 100°C for 1 hour, 150°C for 1 hour, 200°C for 3 hours and 250°C for 1 hour to obtain cured resin M2. Its glass transition temperature was 255°C measured by DMA.
  • the cured sample was polished into a disc (thickness 0.958mm, diameter 3.2cm), and its dielectric properties were measured. The results showed that the dielectric constant was 2.64 and the dielectric loss was 2.00 ⁇ 10 -3 at 5GHz. After soaking in boiling water for 96 hours, the water absorption rate was 0.18%. The dielectric properties of the soaked samples were measured again, and the results showed that the dielectric constant was 2.67 and the dielectric loss was 2.13 ⁇ 10 -3 under the condition of 5GHz.
  • the fluorine-containing siloxane resin (cured resin M4) has lower dielectric constant and dielectric loss than the methoxy-containing polysiloxane resin (cured resin M1). Moreover, the fluorine-containing siloxane resin has a low water absorption rate, and it can still maintain a low dielectric constant and dielectric loss after being soaked in boiling water for 96 hours.
  • the fluorine-containing siloxane resin synthesized in the present invention has excellent performance and can be used as a matrix resin for preparing high-frequency circuit boards.

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Abstract

本发明涉及高频下具有低介电常数和损耗的硅氧烷及其制备方法和应用。具体地，本发明公开了一种硅氧烷单体，以所述单体固化所得树脂在高频下具有低介电常数和低介电损耗、高耐热性、良好加工性和低吸水率，特别适合用于制备高频电路板。

Description

高频下具有低介电常数和损耗的硅氧烷及其制备方法和应用 技术领域
本发明涉及高性能聚合物技术领域，具体地涉及高频下具有低介电常数和损耗的硅氧烷及其制备方法和应用。
背景技术
随着高频通信技术的迅速发展，可作为高频印刷电路板(HPCB)基体树脂的高频低介电材料受到广泛关注。为了满足高频通讯技术的发展要求，低介电材料在高频条件下(>5GHz)应保持低介电常数(D k<2.6)和低介电损耗(D f<2.0×10 -3)。此外，还要求这些材料具有良好的附着力、高耐热性、良好的加工性能以及低吸水率。虽然聚四氟乙烯(PTFE)常用于HPCB制造中，但它对基板的附着力低，不易加工以及热稳定性较低，因此还需要发展综合性能更为优异的低介电材料来替代PTFE以满足应用需求。氰酸酯树脂、环氧树脂、苯并恶嗪树脂等工业树脂由于具有良好的基板附着力和良好的加工性能，长期以来一直被用作印刷电路板的基体树脂。然而这些树脂固化后通常残留有固化剂或添加剂，对材料的介电常数和损耗有不利影响，可以在高频条件下保持较低介电常数和损耗的品种不多。因此，迫切需要开发新型的高频低介电常数材料以满足相关领域的应用需求。
发明内容
本发明的目的在于提供一种高频下具有低介电常数和损耗的硅氧烷(尤其是含氟硅氧烷)及其制备方法和应用。
本发明的第一方面，提供了一种硅氧烷单体，所述单体具有式M所示结构：
Figure PCTCN2021105557-appb-000001
其中，
各R独立地选自下组：氢、卤代或未取代的C1-C15烷基、卤代或未取代的C3-C15环烷基、卤代或未取代的C6-C10芳基；
R a选自下组：取代或未取代的C1-C6烷基、取代或未取代的C2-C6烯基、取代或 未取代的C3-C6环烷基、取代或未取代的C1-C6烷氧基、取代或未取代的C6-C10芳基；其中，所述取代指基团上的一个或多个氢原子被选自下组的一个或多个取代基取代：卤素、卤代或未取代的C1-C4烷基、卤代或未取代的C2-C4烯基、卤代或未取代的C2-C4炔基、卤代或未取代的C1-C4烷氧基、苯基；
X选自下组：氢、卤素、卤代或未取代的C1-C6烷基、卤代或未取代的C1-C6烷氧基。
在另一优选例中，各R相同或不同，优选相同。
在另一优选例中，各R独立地选自下组：卤代或未取代的C1-C12烷基、C3-C10环烷基、苯基；
R a选自下组：C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷基取代的苯基；
X选自下组：卤素、卤代C1-C6烷基、卤代或未取代的C1-C6烷氧基。
在另一优选例中，各R独立地选自下组：氢、甲基、乙基、三氟丙基、苯基、十二烷基。
在另一优选例中，R a选自下组：C1-C6烷基、C2-C6烯基、取代或未取代的苯基；其中，所述取代指基团上的一个或多个氢原子被选自下组的取代基取代：氟原子或其他卤素、三氟甲基、三氟丙基、C1-C6烷氧基、C1-C4烷基。
在另一优选例中，X选自下组：氢、氟、三氟甲基、三氟丙基、C1-C6烷氧基、C1-C4烷基。
在另一优选例中，X选自下组：卤素、卤代C1-C6烷基、卤代C1-C6烷氧基。
在另一优选例中，所述单体选自下组：
Figure PCTCN2021105557-appb-000002
本发明的第二方面，提供了一种本发明第一方面所述的硅氧烷单体的制备方法，包括如下步骤：
Figure PCTCN2021105557-appb-000003
1)在溶剂中，在催化剂存在下，将式A化合物与式B化合物反应得到式M化合物；
其中，R、R a和X如本发明第一方面所定义；
R b为卤代或未取代的C1-C6烷氧基。
在另一优选例中，步骤1)在0-80℃下进行，较佳地5-40℃，更佳地10-35℃。
在另一优选例中，步骤1)的反应时间为0.5-12h，较佳地1-5h，更佳地1.5-3h。
在另一优选例中，所述溶剂选自下组：四氢呋喃、二氯甲烷、甲苯、或其组合。
在另一优选例中，所述催化剂为B(C 6F 5) 3。
在另一优选例中，式A化合物与式B化合物的摩尔比为2-2.5，优选为2。
在另一优选例中，所述催化剂与式B化合物的摩尔比为0.003-0.1，较佳地0.005-0.05。
本发明的第三方面，提供了一种固化树脂，所述固化树脂采用本发明第一方面所述单体固化得到。
在另一优选例中，所述固化树脂具有选自下组的一个或多个特征：
1)所述固化树脂在5GHz条件下的介电常数≤2.9(较佳地≤2.8，更佳地≤2.7，最佳地≤2.6)；
2)所述固化树脂在5GHz条件下的介电损耗≤3×10 -3(较佳地≤2.5×10 -3，更佳地≤2×10 -3)；
3)所述固化树脂的玻璃化转变温度≥200℃(较佳地≥220℃，更佳地≥240℃)；
4)所述固化树脂的吸水率≤0.5％(较佳地≤0.4％，更佳地≤0.1％，最佳地≤0.08％)。
本发明的第四方面，提供了一种本发明第三方面所述的固化树脂的制备方法，包括如下步骤：
1)将本发明第一方面所述单体加热固化，得到本发明第三方面所述的固化树脂。
在另一优选例中，所述加热固化在80-300℃下处理4-10h。
在另一优选例中，所述加热固化是分步进行的：
1-1)在第一温度下固化第一时间；
1-2)在第二温度下固化第二时间；
1-3)在第三温度下固化第三时间；
1-4)在第四温度下固化第四时间，得到所述固化树脂。
在另一优选例中，所述第一温度为80-120℃，所述第一时间为0.8-1.5h。
在另一优选例中，所述第二温度为130-180℃，所述第二时间为0.8-1.5h。
在另一优选例中，所述第三温度为190-230℃，所述第三时间为1.5-5h。
在另一优选例中，所述第四温度为240-300℃，所述第四时间为0.8-1.5h。
在另一优选例中，步骤1)中，同时加入选自下组的单体N以与本发明第一方面所述单体进行共加热固化：二乙烯基二甲基硅烷、四甲基二乙烯基二硅氧烷、四甲基四乙烯基环四硅氧烷、三乙烯基三甲基环三硅氧烷、或其组合。
在另一优选例中，单体N与本发明第一方面所述单体经选自下组的成型工艺预成型后再加热固化：灌模、溶液旋涂、溶液滴涂。
在另一优选例中，所述溶液旋涂或溶液滴涂包括步骤：将本发明第一方面所述单体单独或与单体N溶于有机溶剂中配成溶液，然后进行旋涂或滴涂；所述的溶剂选自下组：甲苯、二甲苯、三甲苯、二苯醚、环己酮、三氯甲烷、丙酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮、三缩乙二醇二甲醚、四缩乙二醇二甲醚、或其组合。
本发明的第五方面，提供了一种本发明第三方面所述的固化树脂的用途，用于制备高频印刷电路板。
本发明的第六方面，提供了一种高频印刷电路板，用于制备所述高频印刷电路 板的基体树脂由本发明第一方面所述硅氧烷单体或包含本发明第一方面所述硅氧烷单体的混合物固化得到。
应理解，在本发明范围内中，本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。
具体实施方式
本发明人经过长期而深入的研究，通过优化制备工艺获得了一种高频下具有低介电常数和损耗的含氟硅氧烷及其制备方法和应用。在此基础上，发明人完成了本发明。
术语
在本发明中，除非特别指出，所用术语具有本领域技术人员公知的一般含义。
在本发明中，术语“卤素”指F、Cl、Br或I。
在本发明中，“C1-C15烷基”是指包括1-15个碳原子的直链或支链的烷基，例如甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、新戊基、特戊基、或类似基团。“C1-C12烷基”、“C1-C6烷基”和“C1-C4烷基”具有类似的含义。
在本发明中，术语“C2-C6烯基”是指具有2-6个碳原子的含有一个双键的直链或支链烯基，非限制性地包括乙烯基、丙烯基、丁烯基、异丁烯基、戊烯基和己烯基等。“C2-C4烯基”具有类似的含义。
在本发明中，术语“C2-C4炔基”是指具有2-4个碳原子的含有一个三键的直链或支链炔基，非限制性地包括乙炔基、丙炔基、丁炔基、异丁炔基等。
在本发明中，术语“C3-C15环烷基”是指在环上具有3-15个碳原子的环状烷基，非限制性地包括环丙基、环丁基、环戊基、环己基、环庚基、环辛基等。“C3-C10环烷基”、“C3-C8环烷基”和“C3-C6环烷基”具有类似的含义。
在本发明中，术语“C1-C6烷氧基”是指具有1-6个碳原子的直链或支链烷氧基，非限制性地包括甲氧基、乙氧基、丙氧基、异丙氧基和丁氧基等。优选为C1-C4烷氧基。
在本发明中，术语“芳环”或“芳基”具有相同的含义，优选为“C6-C10芳基”。术语“C6-C10芳基”是指在环上不含杂原子的具有6-10个碳原子的芳香族环基，如苯基、萘基等。
在本发明中，术语“卤代”是指被卤素取代。
在本发明中，术语“取代”指特定的基团上的一个或多个氢原子被特定的取代基所取代。特定的取代基为在前文中相应描述的取代基，或各实施例中所出现的取代基。除非特别说明，某个取代的基团可以在该基团的任何可取代的位点上具有一个选自特定组的取代基，所述的取代基在各个位置上可以是相同或不同的。本领域技术人员应理解，本发明所预期的取代基的组合是那些稳定的或化学上可实现的组合。所述取代基例如(但并不限于)：卤素、羟基、羧基(-COOH)、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C8环烷基、3-至12元杂环基、芳基、杂芳基、C1-C8醛基、C2-C10酰基、C2-C10酯基、氨基、C1-C6烷氧基、C1-C10磺酰基等。
在本发明中，术语1-6指1、2、3、4、5或6。其他类似术语具有类似含义。
术语“多个”指1、2、3、4、5或6个。
(含氟)硅氧烷及其制备方法
研究发现，聚硅氧烷通常具有较高的介电常数，但其具有良好的加工性能和较高的热稳定性。进一步研究表明，在聚合物中同时存在氟基和大体积基团可以有效地降低材料介电常数和介电损耗。例如，通过在聚硅氧烷中引入全氟环丁烷基团作为主链或侧链，可以有效地降低聚合物的介电常数和介电损耗(D k<2.6和D f<4.0×10 -3)。然而，含全氟环丁烷基团的聚合物由于其单体需要经过多步反应才能制得而导致收率较低，合成难度较大。经进一步研究，本发明人提供了一种较为简便的合成含氟有机硅氧烷树脂的方法。
本发明设计合成一类新型具有苯乙烯交联基团的含氟硅氧烷单体。其中考虑到原料的易得性及合成方法的便捷性，我们从含氟芳基卤代烃出发，采取较温和的反应进行合成。所得树脂固化后在5GHz高频下表现出较低的介电常数和介电损耗，并且具有低的吸水率和良好的耐热性。本发明制备的含氟聚硅氧烷树脂可为高频通讯领域提供新型的制备高频印刷电路板的基体树脂。
本发明涉及一种在高频(大于5G赫兹)条件下具有低介电常数和低介电损耗的含氟硅氧烷树脂及其制备方法。具体而言，是以含氟的乙氧基硅氧烷与含有苯乙烯基交联基团的硅氢烷为原料，在少量的B(C 6F 5) 3催化剂存在下，在甲苯中，通过Piers-Rubinsztajn反应一锅法合成可交联的含氟硅氧烷单体。该单体固化后，得到在大于5G赫兹的高频下，介电常数和介电损耗均表现优异的含氟聚硅氧烷。本发明提出的可交联含氟硅氧烷单体具有很好的加工性能，单体固化后形成的树脂具有优异的耐热性及低吸水率，以及在高频下显现出低的介电常数和介电损耗。本发明所提供的合成方法原料易得、反应条件温和、产率较高，所得到的含氟可 交联硅氧烷可作为低介电常数材料，用于高频通讯、航空航天、国防等领域。
本发明所述式B化合物采用常规方法制备或是如下制备的：
在惰性气体保护下，向反应装置中加入镁屑或镁条、无水四氢呋喃或乙醚、碘和硅烷
Figure PCTCN2021105557-appb-000004
滴加4-卤代含氟苯或4-溴苯甲醚，在0～80℃反应3～30小时，即可获得式B化合物；
Figure PCTCN2021105557-appb-000005
其中，所述的4-卤代含氟苯是4-碘代含氟苯、4-溴代含氟苯和4-氯代含氟苯；其中X选自下组：氟原子，三氟甲基，三氟丙基，C1-C4烷氧基，C1-C4烷基。
所述的镁屑或镁条、无水四氢呋喃或乙醚、碘、
Figure PCTCN2021105557-appb-000006
和4-卤代含氟苯或4-溴苯甲醚的摩尔比为1-1.5:1-12:0.0005-0.01:1-5:1。
与现有技术相比，本发明具有以下主要优点：
(1)本发明涉及一种合成含氟硅氧烷的方法。本发明基于一锅法合成具有交联基团单体，合成步骤反应条件温和，制备工艺简单，产率高，可用于工业化大规模生产。
(2)本发明合成了一系列具有新颖化学结构的聚硅氧烷树脂。将单体直接热固化得到聚硅氧烷树脂，所设计的聚硅氧烷树脂具有良好的加工性能。
(3)本发明所得含氟硅氧烷固化后表现出较高的耐热性和较低的吸水率(<0.18％),并且在5GHz高频条件下表现出良好的介电性能(介电常数低至2.53，介电损耗为1.66×10 -3)。是一种新型高温固化含氟有机硅树脂，可用作高性能树脂基体或封装材料用于高频通讯，大规模集成电路、微电子工业和航空航天等领域中。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数按重量计算。
除非另行定义，文中所使用的所有专业与科学用语与本领域熟练人员所熟悉的意义相同。此外，任何与所记载内容相似或均等的方法及材料皆可应用于本发明方法中。文中所述的较佳实施方法与材料仅作示范之用。
通用测试方法
DMA测试(即动态热机械分析)
动态热机械分析(DMA)由DMA/SDTA861e仪器在加热速率为3℃/min的氮气氛围下测试。
介电性能测试
介电常数和介电损耗由分离介质谐振器(QWED)在频率为5GHz的室温条件下测试。
吸水率测试
将固化后的树脂片在100℃真空条件下干燥至重量恒定，然后在沸水中浸泡数天。根据固化树脂片浸泡后重量的增加来计算其吸水率。
实施例1 含甲氧基硅氧烷单体M1的合成
Figure PCTCN2021105557-appb-000007
向100mL的圆底烧瓶加入20mmol化合物2a、0.1mmol B(C 6F 5) 3、10mL甲苯，在搅拌下滴加溶于10mL甲苯的40mmol二甲基苯乙烯硅氢烷1。滴加完全后，室温下剧烈搅拌2小时。减压除去溶剂，柱层析得到无色透明液体的含甲氧基硅氧烷单体M1，产率为73％。
1H NMR(CDCl 3,400MHz),δ(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(CDCl 3,101MHz),δ(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.
其中反应物2a按常规方法制备。在氮气气体保护下，向250mL干燥的三颈烧瓶加入磁子搅拌、60mmol镁屑、100mL四氢呋喃、60mmol甲基三乙氧基硅烷和一粒碘，再加入50mmol 4-溴苯甲醚，室温搅拌反应12小时。减压除去溶剂后，加入正己烷再次溶解，有析出沉淀。用硅藻土过滤得到滤液，浓缩，纯的2a通过减压蒸馏得到，收率66％。
1H NMR(CDCl 3,400MHz),δ(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(CDCl 3,126MHz),δ(ppm)161.02,135.49,125.75,113.44,58.30,54.81,18.23,-4.17.
实施例2 含氟基硅氧烷单体M2的合成
Figure PCTCN2021105557-appb-000008
实验方法同实施例1，柱层析得到目标含氟硅氧烷单体M2，收率为77％。
1H NMR(CDCl 3,400MHz),δ(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(CDCl 3,101MHz),δ(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.
反应物2b制备方法同实施例1，区别在于：使用4-氟溴苯代替4-溴苯甲醚，2b通过蒸馏纯化，收率62％。
1H NMR(CDCl 3,400MHz),δ(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(CDCl 3,376MHz),δ(ppm)-110.3.
13C NMR(CDCl 3,126MHz),δ(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.
实施例3 含三氟甲基硅氧烷单体M3的合成
Figure PCTCN2021105557-appb-000009
实验方法基本同实施例1，柱层析得到目标含氟硅氧烷单体M3，收率为79％。
1H NMR(CDCl 3,400MHz),δ(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(CDCl 3,376MHz),δ(ppm)-62.81. 13C NMR(CDCl 3,126MHz),δ(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.
反应物2c制备方法同实施例1，区别在于：使用4-溴三氟甲苯代替4-溴苯甲醚，纯的2c通过减压蒸馏得到，收率为45％。
1H NMR(CDCl 3,400MHz),δ(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(CDCl 3,376MHz),δ(ppm)-63.05.
13C NMR(CDCl 3,126MHz),δ(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.
实施例4 含三氟甲基硅氧烷单体M4的合成
Figure PCTCN2021105557-appb-000010
柱层析得到目标含氟硅氧烷单体M4，收率为83％。
1H NMR(CDCl 3,400MHz),δ(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(CDCl 3,376MHz),δ(ppm)-62.84.
13C NMR(CDCl 3,126MHz),δ(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.
反应物2d的合成方法同实施例1，区别在于：使用4-溴三氟甲苯(90mmol)代替50mmol 4-溴苯甲醚，使用四乙氧基硅烷(45mmol)代替甲基三乙氧基硅烷(60mmol)，纯2d通过减压蒸馏得到，收率为60％.
1H NMR(CDCl 3,400MHz),δ(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(CDCl 3,376MHz),δ(ppm)-63.20.
13C NMR(CDCl 3,126MHz)δ(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.
实施例5 含甲氧基硅氧烷树脂M1的固化及性能
取实施例1中制备的目标含甲氧基硅氧烷单体M1放在管式炉内，升温至100℃固化1h，150℃固化1h，200℃固化3h和250℃固化1h，得到固化树脂M1。利用DMA测试其玻璃化转变温度为234℃。将固化后样品打磨成圆片(厚度1.983mm，直径3.2cm)，测定其介电性能，结果表明，5GHz下介电常数为2.78，介电损耗为2.07×10 -2。在沸水中浸泡96h后，测试其吸水率为0.38％。再测定浸泡后的样品的介电性能，结果表明，其在5GHz条件下介电常数为2.78，介电损 耗为2.38×10 -2。
实施例6 含氟硅氧烷树脂M2的固化及性能
取实施例2中制备的目标含氟硅氧烷单体M2放在管式炉内，升温至100℃固化1h，150℃固化1h，200℃固化3h和250℃固化1h，得到固化树脂M2。利用DMA测试其玻璃化转变温度为255℃。将固化后样品打磨成圆片(厚度0.958mm，直径3.2cm)，测定其介电性能，结果表明，5GHz下介电常数为2.64，介电损耗为2.00×10 -3。在沸水中浸泡96h后，测试其吸水率为0.18％。再测定浸泡后的样品的介电性能，结果表明，其在5GHz条件下介电常数为2.67，介电损耗为2.13×10 -3。
实施例7 含三氟甲基硅氧烷树脂M3的固化及性能
取实施例3中制备的目标含三氟甲基硅氧烷单体M3放在管式炉内，升温至100℃固化1h，150℃固化1h，200℃固化3h和250℃固化1h，得到固化树脂M3。利用DMA测试其玻璃化转变温度为218℃。将固化后样品打磨成圆片(厚度1.763mm，直径3.2cm)，测定其介电性能，结果表明，5GHz下介电常数为2.56，介电损耗为2.41×10 -3。在沸水中浸泡96h后，测试其吸水率为0.091％。再测定浸泡后的样品的介电性能，结果表明，其在5GHz条件下介电常数为2.57，介电损耗为2.42×10 -3。
实施例8 含三氟甲基硅氧烷树脂M4的固化及性能
取实施例4中制备的目标含三氟甲基硅氧烷单体M4放在管式炉内，升温至100℃固化1h，150℃固化1h，200℃固化3h和250℃固化1h，得到固化树脂M4。利用DMA测试其玻璃化转变温度为249℃。将固化后样品打磨成圆片(厚度1.701mm，直径3.2cm)，测定其介电性能，结果表明，5GHz下介电常数为2.53，介电损耗为1.66×10 -3。在沸水中浸泡96h后，测试其吸水率为0.061％。再测定浸泡后的样品的介电性能，结果表明，其在5GHz条件下介电常数为2.57，介电损耗为1.82×10 -3。
实施例5-8的性能数据汇总如表1所示。
表1
Figure PCTCN2021105557-appb-000011
从以上实施例可见，含氟硅氧烷树脂(固化树脂M4)相比含甲氧基的聚硅氧烷树脂(固化树脂M1)具有较低的介电常数和介电损耗。并且含氟硅氧烷树脂具有较低的吸水率，在沸水中浸泡96h后其仍旧能保持较低的介电常数和介电损耗。本发明所合成的含氟硅氧烷树脂具有优异的性能，可作为基体树脂用于制备高频电路板。
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (10)

  1. 一种硅氧烷单体，其特征在于，所述单体具有式M所示结构：
    Figure PCTCN2021105557-appb-100001
    其中，
    各R独立地选自下组：氢、卤代或未取代的C1-C15烷基、卤代或未取代的C3-C15环烷基、卤代或未取代的C6-C10芳基；
    R a选自下组：取代或未取代的C1-C6烷基、取代或未取代的C2-C6烯基、取代或未取代的C3-C6环烷基、取代或未取代的C1-C6烷氧基、取代或未取代的C6-C10芳基；其中，所述取代指基团上的一个或多个氢原子被选自下组的一个或多个取代基取代：卤素、卤代或未取代的C1-C4烷基、卤代或未取代的C2-C4烯基、卤代或未取代的C2-C4炔基、卤代或未取代的C1-C4烷氧基、苯基；
    X选自下组：氢、卤素、卤代或未取代的C1-C6烷基、卤代或未取代的C1-C6烷氧基。
  2. 如权利要求1所述的单体，其特征在于，
    各R独立地选自下组：卤代或未取代的C1-C12烷基、C3-C10环烷基、苯基；
    R a选自下组：C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷基取代的苯基；
    X选自下组：卤素、卤代C1-C6烷基、卤代或未取代的C1-C6烷氧基。
  3. 如权利要求1所述的单体，其特征在于，X选自下组：卤素、卤代C1-C6烷基、卤代C1-C6烷氧基。
  4. 如权利要求1所述的单体，其特征在于，所述单体选自下组：
    Figure PCTCN2021105557-appb-100002
    Figure PCTCN2021105557-appb-100003
  5. 一种权利要求1所述的硅氧烷单体的制备方法，其特征在于，包括如下步骤：
    Figure PCTCN2021105557-appb-100004
    1)在溶剂中，在催化剂存在下，将式A化合物与式B化合物反应得到式M化合物；
    其中，R、R a和X如权利要求1所定义；
    R b为卤代或未取代的C1-C6烷氧基。
  6. 如权利要求5所述的方法，其特征在于，所述催化剂为B(C 6F 5) 3。
  7. 一种固化树脂，其特征在于，所述固化树脂采用权利要求1所述单体固化得到。
  8. 一种权利要求7所述的固化树脂的制备方法，其特征在于，包括如下步骤：
    1)将权利要求1所述单体加热固化，得到权利要求7所述的固化树脂。
  9. 一种权利要求7所述的固化树脂的用途，其特征在于，用于制备高频印刷电路板。
  10. 一种高频印刷电路板，其特征在于，用于制备所述高频印刷电路板的基体树脂由权利要求1所述硅氧烷单体或包含权利要求1所述硅氧烷单体的混合物固化得到。
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