WO2015131839A1 - 含六氟环丁基醚和有机硅氧烷的低介电常数聚合物及其制备和应用 - Google Patents

含六氟环丁基醚和有机硅氧烷的低介电常数聚合物及其制备和应用 Download PDF

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WO2015131839A1
WO2015131839A1 PCT/CN2015/073718 CN2015073718W WO2015131839A1 WO 2015131839 A1 WO2015131839 A1 WO 2015131839A1 CN 2015073718 W CN2015073718 W CN 2015073718W WO 2015131839 A1 WO2015131839 A1 WO 2015131839A1
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polymer
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房强
袁超
金凯凯
刁屾
王佳佳
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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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • 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
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups

Definitions

  • the invention belongs to the technical field of high performance polymer manufacturing, in particular, the invention relates to a low dielectric constant polymer containing hexafluorocyclobutyl ether and siloxane with excellent mechanical properties, low water absorption and low dielectric constant. , and its preparation method and application.
  • interlayer low dielectric materials in integrated circuits have used silicon dioxide or silicone based materials. Although these materials have very high thermal stability and thermomechanical properties, their dielectric constants tend to be higher than 3.0, which cannot meet the requirements of high-frequency communication equipment.
  • Polyimide-based materials are excellent in heat resistance, and a film having a low dielectric constant can be obtained by pore formation, and is widely used as a substitute for silica.
  • the glass transition temperature of ordinary polyimides tends to be lower than the processing temperature of integrated circuit boards, and the materials are easily arranged along the metal or silicon surface during the film formation process, so that the polyimide is low-medium.
  • Electrical materials have anisotropy, including anisotropy of heat conduction, shear strength, and dielectric properties.
  • Polyhexafluorocyclobutyl aryl ether materials have been studied since the 1990s because of their excellent heat resistance and photoelectric properties. To date, they have been fully developed as organic photoconductive materials due to their high transmission efficiency and minimal light loss (see Macromolecules 2004, 37, 5724 and Macromolecules 2005, 38, 8278).
  • a trifunctional trifluorovinyl ether-containing structure is used as a prepolymer, and a thermosetting resin having a hexafluorocyclobutyl aryl ether functional group in the main chain is prepared by high-temperature curing. It has been developed and used as a low dielectric constant material (see Mat. Res.
  • the polymer of formula I is in a liquid state, preferably a colorless viscous liquid.
  • the polymer has a number average molecular weight of from 2,300 to 4,600.
  • the polymer has a weight average molecular weight of 4,300 to 8,600.
  • the polymer of formula I can be cured by heating.
  • the polymer of formula I has a curing temperature of from 150 °C to 250 °C.
  • a process for the preparation of a polymer of the formula I according to the first aspect of the invention which comprises the step of using a trifluoroethylene-containing compound of the following formula II in an inert solvent.
  • the organosilicon monomer of the ether unit is subjected to hydrolysis polymerization to obtain a polymer of formula I;
  • R is selected from the group consisting of C1-C4 alkyl; n is as defined above.
  • the hydrolysis polymerization is carried out in a solvent selected from the group consisting of benzene, toluene, xylene, or a combination thereof.
  • the hydrolysis polymerization reaction has a reaction temperature of 0-100 °C.
  • the hydrolysis polymerization reaction time is 5 to 36 hours.
  • the hydrolysis polymerization reaction time is from 12 to 36 hours.
  • the hydrolysis polymerization is carried out in the presence of an acidic catalyst and/or water.
  • the acidic catalyst is selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, formic acid, or a combination thereof.
  • the molar ratio of water, the acidic catalyst and the organosilicon monomer represented by the formula II is from 50 to 100:1 to 10:1 to 10.
  • the silicone monomer of Formula II is prepared by the following steps:
  • X is a halogen; and R is selected from the group consisting of C1-C4 alkyl.
  • the basic catalyst is selected from the group consisting of potassium carbonate, potassium hydroxide, or a combination thereof.
  • the polar aprotic solvent is selected from the group consisting of N-methylpyrrolidone, DMSO, or a combination thereof.
  • the p-halogenated phenol is selected from the group consisting of p-bromophenol, P-chlorophenol, or a combination thereof.
  • the reaction time is 5 to 30 hours.
  • the molar ratio of the p-halogenated phenol to the tetrafluorodibromoethane is from 1:1 to 10.
  • the polar aprotic solvent is acetonitrile.
  • the elimination reaction is carried out in the presence of zinc powder.
  • the reaction time is 5 to 30 hours.
  • the 4-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-1-halobenzene and zinc are The molar ratio of the powder is 1:1 to 5.
  • the polar aprotic solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, or a combination thereof.
  • the reaction in the step (3), is carried out in the presence of magnesium chips.
  • the alkoxy group is a C1-C4 alkoxy group, preferably, the alkoxy group is selected from the group consisting of methoxy or Ethoxy.
  • the 4-(1,2,2-trifluoroethyleneoxy)-1-halobenzene is added in the following manner: after being formulated into a tetrahydrofuran solution Add dropwise.
  • the reaction time is from 12 to 36 hours.
  • the reaction temperature is 0 to 50 °C.
  • a polymer of formula I according to the first aspect of the invention for heat curing to produce a cured polymer.
  • the heat curing temperature is from 150 ° C to 250 ° C.
  • the polymer has a structure as shown in Formula III:
  • the polymer (final cured product) Si-PFCB is a crosslinked network structure.
  • the polymer has one or more of the following characteristics:
  • the polymer has a dielectric constant of ⁇ 2.5, preferably ⁇ 2.4 (measured at 30 MHz);
  • the 5% thermal decomposition temperature of the polymer under nitrogen atmosphere is ⁇ 450 ° C, preferably ⁇ 470 ° C;
  • the hardness of the polymer is ⁇ 0.35 GPa, preferably ⁇ 0.38 GPa;
  • the Young's modulus of the polymer is ⁇ 8.00 GPa, preferably ⁇ 9.00 GPa, more preferably ⁇ 10.00 GPa;
  • the bond strength of the polymer to the silicon wafer is ⁇ 4.5 GPa, preferably ⁇ 4.8 GPa, more preferably ⁇ 4.90 GPa.
  • a process for the preparation of a polymer according to the fourth aspect of the invention which is prepared by heating a polymer of the formula I, thereby obtaining the invention The polymer of the fourth aspect.
  • the heating is carried out at a temperature in the range of 150 to 250 °C.
  • an article comprising a polymer of formula I according to the first aspect of the invention or a polymer according to the fourth aspect of the invention, or A polymer of formula I according to the first aspect of the invention or a polymer according to the fourth aspect of the invention.
  • the article is selected from the group consisting of a low dielectric constant material, a metal wire overcoated insulating material, a polymer sheet, and a polymer film.
  • the article is a heavily doped silicon wafer - a polymeric film according to the fourth aspect of the invention.
  • the article is a glass fiber - a polymer composite as described in the fourth aspect of the invention.
  • the article is a printed circuit board.
  • the article is a polymer sheet or polymer film comprising the polymer of the fourth aspect of the invention, and the article is prepared by the following method:
  • the above polymer sheet or polymer film is heat-cured to obtain a polymer sheet or a polymer film containing the polymer according to the fourth aspect of the invention.
  • the film forming process is spin coating or film forming.
  • the organic solvent is toluene, xylene, trimethylbenzene, diphenyl ether, cyclohexanone, chloroform, acetone, N,N-dimethylformamide, N,N-di Methyl acetamide, dimethyl sulfoxide, N-methylpyrrolidone, or a combination thereof.
  • R is selected from the group consisting of C1-C4 alkyl.
  • X is a halogen; and R is selected from the group consisting of C1-C4 alkyl.
  • the basic catalyst is selected from the group consisting of potassium carbonate, potassium hydroxide, or a combination thereof.
  • the polar aprotic solvent is selected from the group consisting of N-methylpyrrolidone, DMSO, or a combination thereof.
  • the p-halogenated phenol is selected from the group consisting of p-bromophenol, p-chlorophenol, or a combination thereof.
  • the reaction time is 5 to 30 hours.
  • the molar ratio of the p-halogenated phenol to the tetrafluorodibromoethane is from 1:1 to 10.
  • the polar aprotic solvent is acetonitrile.
  • the elimination reaction is carried out in the presence of zinc powder.
  • the reaction time is 5 to 30 hours.
  • the 4-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-1-halobenzene and zinc are The molar ratio of the powder is 1:1 to 5.
  • the polar aprotic solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, or a combination thereof.
  • the reaction in the step (3), is carried out in the presence of magnesium chips.
  • the alkoxy group is a C1-C4 alkoxy group, preferably, the alkoxy group is selected from the group consisting of methoxy or Ethoxy.
  • the 4-(1,2,2-trifluoroethyleneoxy)-1-halobenzene is added in the following manner: after being formulated into a tetrahydrofuran solution Add dropwise.
  • the reaction time is from 12 to 36 hours.
  • the reaction temperature is 0 to 50 °C.
  • the inventors have found through long-term and in-depth research that after the hydrolysis of the organosiloxane containing the trifluorovinyl ether functional group, the obtained prepolymer is directly cured at a high temperature to obtain a novel organosiloxane material having a novel structure.
  • the material has good electrical properties, thermal stability and bonding properties, and is suitable as a high heat resistance, low dielectric constant high performance coating and packaging material for microelectronics industry, aerospace and defense. And other fields. Based on the above findings, the inventors completed the present invention.
  • cured product of a polymer of formula II As used herein, the terms "cured product of a polymer of formula II", "Si-PFCB polymer of the invention” or "low dielectric constant polymer of hexafluorocyclobutyl ether and organosiloxane" are used herein.
  • the polymer of the formula II of the present invention is subjected to heat curing to obtain a polymer, and a preferred structure is as shown in Formula III:
  • halo means that one or more hydrogen atoms on the group are replaced by a halogen atom, wherein the halogen atom is selected from the group consisting of fluorine, chlorine, bromine, and iodine.
  • C1-C4 alkyl refers to a straight or branched alkyl group having from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, Tert-butyl, or a similar group.
  • C1-C4 alkoxy refers to a straight or branched alkoxy group having from 1 to 4 carbon atoms, such as methoxy.
  • Base ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, or the like.
  • the present invention provides a prepolymer which can be used to prepare a low dielectric constant polymer comprising hexafluorocyclobutyl ether and an organosiloxane, said prepolymer being as shown in formula I:
  • the polymer has a number average molecular weight of from 2,300 to 4,600.
  • the polymer has a weight average molecular weight of 4,300 to 8,600.
  • the polymer of formula I can be prepared by hydrolysis polymerization using a monomer, for example:
  • the hydrolysis polymerization is carried out in a solvent selected from the group consisting of benzene, toluene, xylene, or a combination thereof.
  • the reaction temperature of the hydrolysis polymerization reaction is not particularly limited, and it can be carried out, for example, at the reflux temperature of the solvent or at the boiling point of ROH. In a preferred embodiment of the invention, the reaction temperature is from 0 to 100 ° C, preferably from 4 to 95 ° C.
  • the hydrolysis polymerization reaction time is 5 to 20 hours.
  • the hydrolysis polymerization can be carried out in the presence of a catalyst, for example, in a preferred embodiment of the invention, the reaction is carried out in the presence of an acidic catalyst and/or water.
  • the acidic catalyst includes, but is not limited to, an acid selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, formic acid, or a combination thereof.
  • the molar ratio of water, the acidic catalyst and the organosilicon monomer represented by the formula II is from 50 to 100:5 to 10:1.
  • the silicone monomer represented by the formula II can be produced by a conventional method in the art, for example, by the following steps:
  • the basic catalyst is selected from the group consisting of potassium carbonate, potassium hydroxide, or a combination thereof.
  • the polar aprotic solvent is selected from the group consisting of N-methylpyrrolidone, DMSO, or a combination thereof.
  • the p-halogenated phenol is selected from the group consisting of p-bromophenol, p-chlorophenol, or a combination thereof.
  • the reaction time of the step (1) is not particularly limited, and the reaction end point can be determined by a TLC method. In a preferred embodiment of the present invention, the reaction time is 10 to 30 hours.
  • the molar ratio of the p-halogenated phenol to the tetrafluorodibromoethane is from 1:1 to 10.
  • the polar aprotic solvent is not particularly limited, and may preferably be acetonitrile.
  • the elimination reaction can be carried out under optional catalyst catalysis conditions, or under any suitable reaction conditions, for example, under the action of zinc powder.
  • the reaction time of the step (2) is not particularly limited, and the reaction end point can be determined by a TLC method. In a preferred embodiment of the present invention, the reaction time is 5 to 30 hours.
  • the 4-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-1-halobenzene and zinc are The molar ratio of the powder is 1:1 to 5.
  • the polar aprotic solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, or a combination thereof.
  • the reaction in the step (3), is carried out in the presence of magnesium chips.
  • the alkoxy group is a C1-C4 alkoxy group, preferably, the alkoxy group is selected from the group consisting of methoxy or Ethoxy.
  • the 4-(1,2,2-trifluoroethyleneoxy)-1-halobenzene is added in the following manner: after being formulated into a tetrahydrofuran solution Add dropwise.
  • the reaction time is from 12 to 36 hours.
  • the reaction temperature is 0 to 50 °C.
  • the 4-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-1-halobenzene and zinc The molar ratio of the powder is 1:1 to 5.
  • the (or prepolymer) of the polymer of formula I can be heat cured to prepare a low dielectric constant polymer comprising hexafluorocyclobutyl ether and an organosiloxane, a preferred polymer being A polymer as shown in Formula III.
  • thermosetting material Based on the high heat resistance of silicone, easy processing and good adhesion to silicon wafers, and the low dielectric properties of hexafluorocyclobutyl aryl ether, if the two are combined, it is theoretically possible to obtain good heat resistance. Low dielectric constant material with good mechanical properties.
  • the invention is based on the research status of the above low dielectric materials, from molecular design Theoretically, a combination of hexafluorocyclobutyl aryl ether and organosiloxane is used to obtain a thermosetting material.
  • the present invention provides a polymer (i.e., the Si-PFCB polymer of the present invention) prepared by heat-curing a polymer of the above formula I.
  • a polymer i.e., the Si-PFCB polymer of the present invention
  • a preferred structure of the polymer is as shown in Formula III:
  • the Si-PFCB polymer of the invention is a crosslinked network structure.
  • the polymer has one or more of the following characteristics:
  • the polymer has a dielectric constant of ⁇ 2.5, preferably ⁇ 2.4 (measured at 30 MHz);
  • the 5% thermal decomposition temperature of the polymer under nitrogen atmosphere is ⁇ 450 ° C, preferably ⁇ 470 ° C;
  • the hardness of the polymer is ⁇ 0.35 GPa, preferably ⁇ 0.38 GPa;
  • the Young's modulus of the polymer is ⁇ 8.00 GPa, preferably ⁇ 9.00 GPa, more preferably ⁇ 10.00 GPa;
  • the bond strength of the polymer to the silicon wafer is ⁇ 4.5 GPa, preferably ⁇ 4.8 GPa, more preferably ⁇ 4.90 GPa.
  • the polymer is preferably prepared by the following method:
  • the polymer as shown in Formula I is heated to obtain the Si-PFCB polymer of the present invention.
  • the Si-PFCB polymer of the present invention is prepared by the above method, and has a simple preparation method and excellent properties of the obtained polymer.
  • the heating conditions are not particularly limited, and it is preferably heated at a temperature ranging from 150 to 250 °C.
  • the polymer of formula I according to the first aspect of the invention and the polymer of the fourth aspect of the invention may be used to prepare a series of articles, in another preferred embodiment, the article is selected from the group consisting of: low dielectric Constant material, gold
  • the wire is covered with an insulating material, a polymer sheet, and a polymer film.
  • a preferred class of articles are articles containing the Si-PFCB polymer of the present invention, and the articles are preferably prepared by molding with a polymer of formula I to obtain a preform, and then The preform is heat-cured to obtain a product containing the Si-PFCB polymer of the present invention.
  • the article containing the Si-PFCB polymer of the present invention is a polymer sheet or a polymer film, and the article is prepared by the following method
  • the polymer sheet is obtained by molding at room temperature with a polymer of the formula I; or dissolving the polymer of the formula I with an organic solvent and forming a film to obtain a polymer film, and then heating and curing the polymer sheet or the polymer film.
  • a polymer sheet or a polymer film containing the Si-PFCB polymer of the present invention is obtained.
  • the film forming process is spin coating or film forming.
  • the organic solvent is toluene, xylene, trimethylbenzene, diphenyl ether, cyclohexanone, chloroform, acetone, N,N-dimethylformamide, N,N-di Methyl acetamide, dimethyl sulfoxide, N-methylpyrrolidone, or a combination thereof.
  • the Si-PFCB polymer provided by the present invention has excellent electrical properties and heat resistance, and the Si-PFCB polymer of the present invention prepared in a preferred embodiment of the present invention has a dielectric constant as low as 2.33. (30MHz), 5% thermal decomposition temperature of 471 ° C, hardness of 0.392 GPa, Young's modulus of 10.06 GPa, and bonding strength with silicon wafers of 4.93 GPa.
  • the low dielectric material provided by the invention has low synthesis cost, simple preparation process, and can be used as a high-performance electronic packaging material or metal wire outsourcing with excellent thermal stability, low water absorption rate and low dielectric constant.
  • the coating is applied in the fields of microelectronics processing industry and large motor manufacturing.
  • the prepolymer provided by the invention can be used for preparing a polymer having good electrical properties, heat resistance and mechanical properties, and has a simple preparation method and is suitable for industrial production.
  • the concentrate was rectified to yield a product of <RTIgt;</RTI> Atmospheric boiling point 246 ⁇ 256 ° C, hydrogen characterization ( 1 H NMR, 300 MHz, CDCl 3 , ⁇ in ppm): 7.51 ⁇ 7.53 (d, 2H), 7.11 ⁇ 7.13 (d, 2H); Fluorescence characterization ( 19 F NMR , 282 MHz, CDCl 3 , ⁇ inppm): -86.2, (dt, 2F) - 68.2 (dt, 2F).
  • Example 2 Under argon protection, 76 g of 4-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-bromobenzene (0.22 mol) obtained in Example 2 was added to the reaction flask, 480 ml. The acetonitrile was newly distilled, diluted by stirring, and 30 g of zinc powder (0.5 mol) was added, and the mixture was heated under reflux for 24 hours. The reaction solution was poured into 600 ml of water, stirred for 15 minutes or more, and extracted with chloroform in portions, and the chloroform extracts were combined, washed with a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate over 12 hr.
  • the chloroform was removed by rotary distillation, and the concentrate was subjected to distillation to collect 56.2 ° C / 0.6 mmHg of the product to obtain 43.8 g of a yield of 61%.
  • the atmospheric boiling point of the product is 242-252 ° C, hydrogen characterization ( 1 H NMR, 300 MHz, CDCl 3 , ⁇ inppm): 7.47 ⁇ 7.49 (d, 2H), 6.99 ⁇ 7.01 (d, 2H); fluorine spectrum characterization ( 19 F NMR, 282 MHz, CDCl 3 , ⁇ in ppm): -134.2 to -134.7 (dd, 1F), -126.4 to -125.8 (dd, 1F), -119.4 to -119.0 (dd, 1F).
  • the atmospheric boiling point of the product is 258-262 ° C, hydrogen characterization ( 1 H NMR, 300 MHz, CDCl 3 , ⁇ in ppm): 7.64 ⁇ 7.66 (d, 2H), 7.10 ⁇ 7.12 (d, 2H), 3.79 ⁇ 3.82 (q , 4H), 1.22 to 1.25 (t, 6H), 0.35 (s, 3H); Fluorescence characterization ( 19 F NMR, 282 MHz, CDCl 3 , ⁇ in ppm): -133.8 to -134.2 (dd, 1F), -126.2 ⁇ -126.7 (dd, 1F), -119.4 to -119.9 (dd, 1F); carbon characterization ( 13 C NMR, 75 MHz, CDCl 3 , ⁇ in ppm): 156.7, 136.1, 131.5, 129.7, 115.2, 111.4, 58.3 , 18.0, -4.4.
  • Example 6 0.5 g of the prepolymer obtained in Example 6 was dissolved in 15 ml of toluene, and the obtained solution was filtered through a 2 ⁇ m filter, and then dripped at a temperature of 1000-4000 rpm to a strictly cleaned heavy blend at room temperature. On the silicon wafer (resistivity 2 ⁇ 10 -3 ⁇ .cm). After the surface-flattened film was obtained by spin coating, it was placed in a nitrogen-protected tube furnace, and the solvent was first removed at 150 ° C for 3 hours, and then heated to 180 ° C for 18 hours or at 250 ° C for 4 hours. The cured film was thus obtained.
  • the polymer film having a thickness of 170 nm prepared in Example 7 was placed in a vacuum drying oven, heated at 200 ° C for 2 hours, and cooled to room temperature in a nitrogen atmosphere, and an aluminum having a diameter of 1 mm was deposited on the surface of the film.
  • the electrode was vapor-deposited with a metal nano-thickness of 200 nm on the back side of the silicon wafer, thus obtaining a standard film capacitor.
  • the dielectric constant and dielectric loss factor of the film were calculated by testing the capacitance of the film capacitor.
  • the film obtained by the above spin coating method was pulverized, placed in a thermogravimetric analyzer, and the thermal decomposition temperature and the amount of residual carbon of the polymer were measured at a heating rate of 10 ° C / min.
  • the above-mentioned film obtained by spin coating was subjected to nanomechanical testing by a nano-composite mechanical system to obtain nano hardness, Young's modulus and bonding strength.
  • Example 9 Use of a polymer as a printed circuit board insulating resin
  • Example 6 50 g of the prepolymer obtained in Example 6 was dissolved in 200 ml of toluene, and the solution was brushed with a brush to an alkali-free glass cloth previously treated with a silane coupling agent KH550 (600 g/m) at room temperature. 2 ), after removing the solvent at 120 ° C for 3 hours, the obtained glass fiber prepreg laminate (4 layers) was placed in a flat vulcanizer, and press molded at a pressure of 20 kg/cm 2 and a temperature of 180 °C. The formed fiberglass board was held at 250 ° C for 4 hours to obtain a cured glass fiber composite material which can be directly used for the manufacture of printed circuit boards.
  • a silane coupling agent KH550 600 g/m
  • the obtained fiberglass board has a water absorption rate of 0.12%, a dielectric constant of 2.8 at an operating frequency (50 Hz) of an electric device, and a dielectric loss tangent of 4 ⁇ 10 -3 , which is lower than that currently used in the industry.
  • a glass fiber reinforced composite material prepared by using a polyimide or the like as a matrix resin.

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Abstract

本发明涉及含六氟环丁基醚和有机硅氧烷的低介电常数聚合物及其制备和应用，具体地，本发明提供了一种用如式I所示的聚合物进行加热固化所形成的聚合物，及其制备方法和用途。所述的聚合物具有良好的电学性能和耐热性，且制备方法简单，适用于电子电气行业作为绝缘包覆层和电子元器件的封装材料。

Description

含六氟环丁基醚和有机硅氧烷的低介电常数聚合物及其制备和应用 技术领域
本发明属于高性能聚合物制造技术领域，具体地，本发明涉及一种力学性能优异、低吸水率和低介电常数的含六氟环丁基醚和硅氧烷的低介电常数聚合物，及其制备方法和应用。
背景技术
传统上，集成电路中的层间低介电材料采用二氧化硅或有机硅类材料。这些材料虽然具有非常高的热稳定性和热机械性能，但其介电常数往往高于3.0，不能满足高频通讯设备的要求。聚酰亚胺类材料因耐热性良好，通过造孔，可以获得介电常数较低的薄膜，作为二氧化硅的替代品而被广泛应用。然而，普通的聚酰亚胺的玻璃化转变温度往往低于集成电路板的加工温度，并且该材料在成膜过程中易沿金属或硅表面进行有序排列，从而使得聚酰亚胺低介电材料具有各向异性，其中包括热传导、耐剪切强度和介电性能的各向异性。因此，工业部门和研究院所进一步开发了许多有机聚合物类低介电材料。但是，这些材料通常热稳定性不足，与金属或硅的表面粘结性差。随着微电子工业的发展，基于铜互连技术的90纳米芯片的制造业对材料工业提出诸多需求，以上所述的纯粹的含硅和有机聚合物将面临逐渐被淘汰的局面。人们所面临的最迫切的问题是，需要开发出既具有低介电常数又有高的耐热性的材料。
聚六氟环丁基芳基醚类材料因其具有优异的耐热性和光电性能，从20世纪90年代起，人们就对其进行了研究。迄今，由于具有较高的传输效率和极小的光损失，它们已经被充分开发用作有机光导材料(参见Macromolecules 2004,37,5724和Macromolecules 2005,38,8278)。另一方面，因为C-F键具有较小的可极化率，以三官能度含三氟乙烯基醚结构为预聚体，通过高温固化制备出主链含有六氟环丁基芳基醚官能团的热固性树脂已被开发并用作低介电常数材料(见Mat.Res.Soc.Symp.Proc.1997,443,177)。近年来，源于四氟乙烯的全氟环丁烷基芳基醚(polyperfluorocyclobutane，PFCB)类聚合物受到人们高度重视，原因是，这类聚合物不仅成本相对较低，而且具有优异的电学性能及低吸湿率(见WO9015043)。但是，完全基于PFCB有机骨架结构的低介电材料的热稳定性和粘结性能不足。 因此，致力于改进并消除这些缺陷是很有必要的。
发明内容
本发明的目的是提供一种热稳定性和粘结性能改善的PFCB有机骨架结构的低介电材料。
本发明的第一方面，提供了一种如式I所示的聚合物：
Figure PCTCN2015073718-appb-000001
式中，n≥2；较佳地，n＝5～100；更佳地，n＝10～20。
在另一优选例中，所述的式I聚合物为液态，较佳地为无色黏稠液体。
在另一优选例中，所述聚合物的数均分子量为2,300～4,600。
在另一优选例中，所述聚合物的重均分子量为4,300～8,600。
在另一优选例中，所述的式I聚合物可以加热固化，较佳地，所述的式I聚合物的固化温度为150℃～250℃。
本发明的第二方面，提供了一种如本发明第一方面所述的式I聚合物的制备方法，所述方法包括步骤：在惰性溶剂中，用如下式II所示的含三氟乙烯基醚单元的有机硅单体进行水解聚合反应，得到式I聚合物；
Figure PCTCN2015073718-appb-000002
其中，R选自下组：C1-C4烷基；n的定义如上文中所述。
在另一优选例中，所述的水解聚合反应在选自下组的溶剂中进行：苯、甲苯、二甲苯，或其组合。
在另一优选例中，所述的水解聚合反应的反应温度为0-100℃。
在另一优选例中，所述的水解聚合反应时间为5～36小时。
在另一优选例中，所述的水解聚合反应时间为12～36小时。
在另一优选例中，所述的水解聚合反应酸性催化剂和/或水存在下进行。
在另一优选例中，所述的酸性催化剂选自下组：盐酸、硫酸、乙酸、甲酸，或其组合。
在另一优选例中，所述的水解聚合反应中，水、酸性催化剂和式II所示的有机硅单体的摩尔比为50～100：1～10:1～10。
在另一优选例中，所述的式II所示的有机硅单体是通过下述步骤制备的：
(1)在极性非质子性溶剂中，在碱性催化剂存在下，用对卤代苯酚与四氟二溴乙烷于室温下反应，制备4-(2-溴-1,1,2,2-四氟乙氧基)-1-卤代苯；
Figure PCTCN2015073718-appb-000003
(2)在极性非质子性溶剂中，将所述的4-(2-溴-1,1,2,2-四氟乙氧基)-1-1-卤代苯进行消去反应，得到4-(1,2,2-三氟乙烯氧基)-1-卤代苯；
Figure PCTCN2015073718-appb-000004
(3)在极性非质子性溶剂中，用甲基三烷氧基硅烷与4-(1,2,2-三氟乙烯氧基)-1-卤代苯反应，得到如式II所示的有机硅单体；
Figure PCTCN2015073718-appb-000005
上述各式中，X为卤素；R选自下组：C1-C4烷基。
在另一优选例中，在所述步骤(1)中，所述的碱性催化剂选自下组：碳酸钾、氢氧化钾，或其组合。
在另一优选例中，在所述步骤(1)中，所述的极性非质子性溶剂选自下组：N-甲基吡咯烷酮、DMSO，或其组合。
在另一优选例中，在所述步骤(1)中，所述的对卤代苯酚选自下组：对溴苯酚、 对氯苯酚，或其组合。
在另一优选例中，在所述步骤(1)中，所述的反应时间为5～30小时。
在另一优选例中，在所述步骤(1)中，所述的对卤代苯酚和四氟二溴乙烷的摩尔比为1:1～10。
在另一优选例中，在所述步骤(2)中，所述的极性非质子性溶剂为乙腈。
在另一优选例中，在所述步骤(2)中，所述的消去反应在在锌粉存在下进行。
在另一优选例中，在所述步骤(2)中，所述的反应时间为5～30小时。
在另一优选例中，在所述步骤(2)中，所述的4-(2-溴-1,1,2,2-四氟乙氧基)-1-1-卤代苯和锌粉的摩尔比为1：1～5。
在另一优选例中，在所述步骤(3)中，所述的极性非质子性溶剂选自下组：四氢呋喃、乙醚，或其组合。
在另一优选例中，在所述步骤(3)中，所述的反应在镁屑存在下进行。
在另一优选例中，在所述步骤(3)中，所述的烷氧基为C1-C4的烷氧基，较佳地，所述的烷氧基选自下组：甲氧基或乙氧基。
在另一优选例中，在所述步骤(3)中，所述的4-(1,2,2-三氟乙烯氧基)-1-卤代苯通过以下方式加入：配制为四氢呋喃溶液后滴加。
在另一优选例中，在所述步骤(3)中，所述的反应时间为12～36小时。
在另一优选例中，在所述步骤(3)中，所述的反应温度为0-50℃。
本发明的第三方面，提供了一种如本发明第一方面所述的式I聚合物用于进行加热固化，从而制备固化聚合物的用途。
在另一优选例中，所述的加热固化温度为150℃～250℃。
本发明的第四方面，提供了一种聚合物，所述的聚合物是用如式I所述的聚合物进行固化制备的：较佳地，所述的固化为加热固化。
在另一优选例中，所述的聚合物具有如式III所示的结构：
Figure PCTCN2015073718-appb-000006
式中，m为正整数，且m≤n。
在另一优选例中，所述的聚合物(最终的固化产物)Si-PFCB为交联的网状结构。
在另一优选例中，所述的聚合物具有以下的一个或多个特征：
所述聚合物的介电常数为≤2.5，较佳地为≤2.4(在30 MHz下测定)；
在氮气气氛下，所述聚合物的5％热分解温度为≥450℃，较佳地为≥470℃；
所述聚合物的硬度为≥0.35 GPa，较佳地为≥0.38 GPa；
所述聚合物的杨氏模量为≥8.00 GPa，较佳地为≥9.00 GPa，更佳地为≥10.00GPa；
所述聚合物与硅片的结合强度为≥4.5 GPa，较佳地为≥4.8 GPa，更佳地为≥4.90 GPa。
本发明的第五方面，提供了一种如本发明第四方面所述的聚合物的制备方法，所述聚合物通过以下方法制备：加热如式I所示的聚合物，从而得到如本发明第四方面所述的聚合物。
在另一优选例中，所述加热的温度范围为150～250℃。
本发明的第六方面，提供了一种制品，所述制品含有如本发明第一方面所述的式I聚合物或如本发明第四方面所述的聚合物，或所述制品是用如本发明第一方面所述的式I聚合物或如本发明第四方面所述的聚合物制备的。
在另一优选例中，所述的制品选自下组：低介电常数材料、金属导线外包覆绝缘材料、聚合物片材、聚合物薄膜。
在另一优选例中，所述的制品为重掺杂硅片-如本发明第四方面所述的聚合物薄膜。
在另一优选例中，所述的制品为玻璃纤维-如本发明第四方面所述的聚合物复合材料。
在另一优选例中，所述的制品为印刷电路板。
在另一优选例中，所述的制品为含有本发明第四方面所述的聚合物的聚合物片材或聚合物薄膜，且所述的制品是通过以下方法制备的：
用本发明第一方面所述的式I聚合物进行室温模压得到含有式I聚合物的片材；或用有机溶剂溶解所述式I聚合物并进行成膜，得到含有式I聚合物的膜；
对上述聚合物片材或聚合物膜进行加热固化，得到含有如本发明第四方面所述的聚合物的聚合物片材或聚合物薄膜。
在另一优选例中，所述的成膜工艺为旋涂成膜或滴涂成膜。
在另一优选例中，所述的有机溶剂为甲苯、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，或其组合。
本发明的第七方面，提供了一种如下式II所示的有机硅单体：
Figure PCTCN2015073718-appb-000007
其中，R选自下组：C1-C4烷基。
本发明的第八方面，提供了一种如本发明第七方面所述的有机硅单体的制备方法，通过下述步骤制备：
(1)在极性非质子性溶剂中，在碱性催化剂存在下，用对卤代苯酚与四氟二溴乙烷于室温下反应，制备4-(2-溴-1,1,2,2-四氟乙氧基)-1-卤代苯；
Figure PCTCN2015073718-appb-000008
(2)在极性非质子性溶剂中，将所述的4-(2-溴-1,1,2,2-四氟乙氧基)-1-1-卤代苯进行消去反应，得到4-(1,2,2-三氟乙烯氧基)-1-卤代苯；
Figure PCTCN2015073718-appb-000009
(3)在极性非质子性溶剂中，用甲基三烷氧基硅烷与4-(1,2,2-三氟乙烯氧基)-1-卤代苯反应，得到如式II所示的有机硅单体；
Figure PCTCN2015073718-appb-000010
上述各式中，X为卤素；R选自下组：C1-C4烷基。
在另一优选例中，在所述步骤(1)中，所述的碱性催化剂选自下组：碳酸钾、氢氧化钾，或其组合。
在另一优选例中，在所述步骤(1)中，所述的极性非质子性溶剂选自下组：N-甲基吡咯烷酮、DMSO，或其组合。
在另一优选例中，在所述步骤(1)中，所述的对卤代苯酚选自下组：对溴苯酚、对氯苯酚，或其组合。
在另一优选例中，在所述步骤(1)中，所述的反应时间为5～30小时。
在另一优选例中，在所述步骤(1)中，所述的对卤代苯酚和四氟二溴乙烷的摩尔比为1:1～10。
在另一优选例中，在所述步骤(2)中，所述的极性非质子性溶剂为乙腈。
在另一优选例中，在所述步骤(2)中，所述的消去反应在在锌粉存在下进行。
在另一优选例中，在所述步骤(2)中，所述的反应时间为5～30小时。
在另一优选例中，在所述步骤(2)中，所述的4-(2-溴-1,1,2,2-四氟乙氧基)-1-1-卤代苯和锌粉的摩尔比为1：1～5。
在另一优选例中，在所述步骤(3)中，所述的极性非质子性溶剂选自下组：四氢呋喃、乙醚，或其组合。
在另一优选例中，在所述步骤(3)中，所述的反应在镁屑存在下进行。
在另一优选例中，在所述步骤(3)中，所述的烷氧基为C1-C4的烷氧基，较佳地，所述的烷氧基选自下组：甲氧基或乙氧基。
在另一优选例中，在所述步骤(3)中，所述的4-(1,2,2-三氟乙烯氧基)-1-卤代苯通过以下方式加入：配制为四氢呋喃溶液后滴加。
在另一优选例中，在所述步骤(3)中，所述的反应时间为12～36小时。
在另一优选例中，在所述步骤(3)中，所述的反应温度为0-50℃。
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发现，含三氟乙烯基醚官能团的有机硅氧烷经过水解后，所获得的预聚物经直接高温固化，可获得一种结构新颖的有机硅氧烷材料。所述的材料具有较好的电学性能、热稳定性和粘结性能，适合作为一种高耐热、低介电常数的高性能涂层和封装材料，应用于微电子工业、航空航天和国防等领域。基于上述发现，发明人完成了本发明。
术语
如本文所用，术语“式II聚合物的固化产物”、“本发明的Si-PFCB聚合物”或“含六氟环丁基醚和有机硅氧烷的低介电常数聚合物”均指用本发明的式II聚合物进行加热固化所制备的聚合物，一种优选的结构如式III所示：
Figure PCTCN2015073718-appb-000011
除非特别说明，术语“卤代”指基团上的一个或多个氢原子被卤素原子所取代，其中，所述的卤素原子选自下组：氟、氯、溴、碘。
术语“C1-C4烷基”指具有1～4个碳原子的直链或支链烷基，例如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、或类似基团。
术语“C1-C4烷氧基”指具有1-4个碳原子的直链或支链烷氧基，例如甲氧 基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、仲丁氧基、叔丁氧基、或类似基团。
含氟硅氧烷预聚体
本发明提供了一种可以用于制备含六氟环丁基醚和有机硅氧烷的低介电常数聚合物的预聚体，所述的预聚体如式I所示：
Figure PCTCN2015073718-appb-000012
式中，n≥2；较佳地，n＝5～100；更佳地，n＝10～20。
在另一优选例中，所述聚合物的数均分子量为2,300～4,600。
在另一优选例中，所述聚合物的重均分子量为4,300～8,600。
本发明的优选例中，所述的式I聚合物可以用单体进行水解聚合制备，例如：
在惰性溶剂中，用如下式II所示的含三氟乙烯基醚单元的有机硅单体进行水解聚合反应，得到式I聚合物；
Figure PCTCN2015073718-appb-000013
其中，R选自下组：C1-C4烷基；n≥2；较佳地，n＝5～100；更佳地，n＝10～20。
在另一优选例中，所述的水解聚合反应在选自下组的溶剂中进行：苯、甲苯、二甲苯，或其组合。
所述的水解聚合反应的反应温度没有特别限制，例如可以在溶剂的回流温度下，或在ROH的沸点下进行。在本发明的优选例中，所述的反应温度为0-100℃，较佳地为4-95℃。
在另一优选例中，所述的水解聚合反应时间为5～20小时。
所述的水解聚合反应可以在催化剂存在下进行，例如，在本发明的一个优选例中，所述的反应在酸性催化剂和/或水存在下进行。其中，所述的酸性催化剂包括(但并不限于)选自下组的酸：盐酸、硫酸、乙酸、甲酸，或其组合。
在另一优选例中，所述的水解聚合反应中，水、酸性催化剂和式II所示的有机硅单体的摩尔比为50～100：5～10:1。
所述的式II所示的有机硅单体可以通过本领域的常规方法制备，例如，可以通过下述步骤制备：
Figure PCTCN2015073718-appb-000014
(1)在极性非质子性溶剂中，在碱性催化剂存在下，用对卤代苯酚与四氟二溴乙烷于室温下反应，制备4-(2-溴-1,1,2,2-四氟乙氧基)-1-卤代苯；
在另一优选例中，在所述步骤(1)中，所述的碱性催化剂选自下组：碳酸钾、氢氧化钾，或其组合。
在另一优选例中，在所述步骤(1)中，所述的极性非质子性溶剂选自下组：N-甲基吡咯烷酮、DMSO，或其组合。
在另一优选例中，在所述步骤(1)中，所述的对卤代苯酚选自下组：对溴苯酚、对氯苯酚，或其组合。
所述步骤(1)的反应时间没有特别限制，可以通过TLC法确定反应终点，在本发明的一个优选例中，所述的反应时间为10～30小时。
在另一优选例中，在所述步骤(1)中，所述的对卤代苯酚和四氟二溴乙烷的摩尔比为1:1～10。
Figure PCTCN2015073718-appb-000015
(2)在极性非质子性溶剂中，将所述的4-(2-溴-1,1,2,2-四氟乙氧基)-1-1-卤代苯进行消去反应，得到4-(1,2,2-三氟乙烯氧基)-1-卤代苯；
其中，所述的极性非质子性溶剂没有特别限制，较佳地可以为乙腈。
所述的消去反应可以在任选的催化剂催化条件，或者在任意合适的反应条件下进行，例如，可以在锌粉作用下进行。
所述步骤(2)的反应时间没有特别限制，可以通过TLC法确定反应终点，在本发明的一个优选例中，所述的反应时间为5～30小时。
在另一优选例中，在所述步骤(2)中，所述的4-(2-溴-1,1,2,2-四氟乙氧基)-1-1-卤代苯和锌粉的摩尔比为1：1～5。
Figure PCTCN2015073718-appb-000016
(3)在极性非质子性溶剂中，用甲基三烷氧基硅烷与4-(1,2,2-三氟乙烯氧基)-1-卤代苯反应，得到如式II所示的有机硅单体。
在另一优选例中，在所述步骤(3)中，所述的极性非质子性溶剂选自下组：四氢呋喃、乙醚，或其组合。
在另一优选例中，在所述步骤(3)中，所述的反应在镁屑存在下进行。
在另一优选例中，在所述步骤(3)中，所述的烷氧基为C1-C4的烷氧基，较佳地，所述的烷氧基选自下组：甲氧基或乙氧基。
在另一优选例中，在所述步骤(3)中，所述的4-(1,2,2-三氟乙烯氧基)-1-卤代苯通过以下方式加入：配制为四氢呋喃溶液后滴加。
在另一优选例中，在所述步骤(3)中，所述的反应时间为12～36小时。
在另一优选例中，在所述步骤(3)中，所述的反应温度为0-50℃。
在另一优选例中，在所述步骤(3)中，所述的4-(2-溴-1,1,2,2-四氟乙氧基)-1-1-卤代苯和锌粉的摩尔比为1：1～5。
所述的式I聚合物的(或预聚体)可以进行加热固化，从而制备含六氟环丁基醚和有机硅氧烷的低介电常数聚合物，一种优选的所述聚合物是如式III所示的聚合物。
含六氟环丁基醚和有机硅氧烷的低介电常数聚合物
基于有机硅的高耐热性、易加工性和与硅片的良好粘结性，以及六氟环丁基芳基醚的低介电性能，如将两者结合起来，理论上可以获得耐热性好、力学性能佳的低介电常数材料。本发明正是基于上述低介电材料的研究现状，从分子设计 理论出发，将六氟环丁基芳基醚和有机硅氧烷结合起来获得热固性的材料。
具体地，本发明提供了一种用上述式I聚合物进行加热固化，从而制备的聚合物(即本发明的Si-PFCB聚合物)。一种优选的所述聚合物的结构如式III所示：
Figure PCTCN2015073718-appb-000017
式中，m为正整数，且m≤n。
在优选的本发明实施例中，本发明的Si-PFCB聚合物为交联的网状结构。
在另一优选例中，所述的聚合物具有以下的一个或多个特征：
所述聚合物的介电常数为≤2.5，较佳地为≤2.4(在30 MHz下测定)；
在氮气气氛下，所述聚合物的5％热分解温度为≥450℃，较佳地为≥470℃；
所述聚合物的硬度为≥0.35 GPa，较佳地为≥0.38 GPa；
所述聚合物的杨氏模量为≥8.00 GPa，较佳地为≥9.00 GPa，更佳地为≥10.00GPa；
所述聚合物与硅片的结合强度为≥4.5 GPa，较佳地为≥4.8 GPa，更佳地为≥4.90 GPa。
在本发明中，所述的聚合物优选地通过以下方法制备：
加热如式I所示的聚合物，从而得到本发明的Si-PFCB聚合物。用上述方法制备本发明的Si-PFCB聚合物，具有制备方法简单，制得的聚合物性能优异的特点。
所述加热的条件没有特别的限制，较佳地，在温度范围为150～250℃下加热。
含六氟环丁基醚和有机硅氧烷的低介电常数聚合物的应用
本发明第一方面所述的式I聚合物和本发明第四方面所述的聚合物可以用于制备一系列制品，在另一优选例中，所述的制品选自下组：低介电常数材料、金 属导线外包覆绝缘材料、聚合物片材、聚合物薄膜。
其中，一类优选的制品为含有本发明的Si-PFCB聚合物的制品，且所述的制品优选地是通过以下方法制备的：用式I聚合物进行成型，得到预成型体，然后对所述预成型体进行加热固化，得到含有本发明的Si-PFCB聚合物的制品。
在本发明的一个优选例中，所述的含有本发明的Si-PFCB聚合物的制品为聚合物片材或聚合物薄膜，且所述的制品是通过以下方法制备
用式I聚合物进行室温模压得到聚合物片材；或用有机溶剂溶解所述式I聚合物并进行成膜得到聚合物薄膜，然后对所述的聚合物片材或聚合物薄膜进行加热固化，得到含有本发明的Si-PFCB聚合物的聚合物片材或聚合物薄膜。
在另一优选例中，所述的成膜工艺为旋涂成膜或滴涂成膜。
在另一优选例中，所述的有机溶剂为甲苯、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，或其组合。
本发明的主要优点包括：
(1)本发明提供的Si-PFCB聚合物具有很好的电学性能和耐热性，在本发明的一个优选例中所制备的本发明的Si-PFCB聚合物具有低达2.33的介电常数(30MHz)，5％热分解温度达471℃，硬度为0.392 GPa，杨氏模量为10.06 GPa，与硅片的结合强度为4.93 GPa。
(2)本发明所提供的低介电材料合成成本较低，制备过程简单，可作为一类具有优异热稳定性、低吸水率和低介电常数的高性能电子封装材料或金属导线外包覆层，应用于微电子加工业和大电机制造业等领域。
(3)本发明所提供的预聚体可用于制备具有很好的电学性能、耐热性能和力学性能的聚合物，且制备方法简单，适合工业化生产。
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。
实施例1中间体14-(2-溴-1,1,2,2-四氟乙氧基)-1-溴苯的制备
Figure PCTCN2015073718-appb-000018
氩气保护下，在反应装置中加入51.9克4-溴-苯酚(0.3 mol)，147克1,2-二溴四氟乙烷(0.57 mol)和300毫升现蒸的DMSO(二甲基亚砜)，冰水浴下搅拌30分钟，然后加入80克无水碳酸钾(0.6 mol)，撤去冰水浴，室温反应6小时，将反应混合溶液倒入水中，剧烈搅拌20分钟，分批次用氯仿将产物萃取，萃取液用饱和氯化钠水溶液洗后旋蒸除去氯仿，浓缩液精馏收集65℃/0.23mmHg组分得产物98克，收率93％。常压沸点226～246℃，氢谱表征(1H NMR，300MHz,CDCl3,δin ppm):7.51～7.53(d,2H),7.11～7.13(d,2H)；氟谱表征(19F NMR，282MHz,CDCl3,δinppm):-86.2,(dt,2F)-68.2(dt,2F)。
实施例2中间体14-(2-溴-1,1,2,2-四氟乙氧基)-1-溴苯的制备
Figure PCTCN2015073718-appb-000019
氩气保护下，在反应装置中加入51.9克4-溴-苯酚(0.3 mol)，147克1,2-二溴四氟乙烷(0.57 mol)和300毫升现蒸的N-甲基吡咯烷酮，冰水浴下搅拌30分钟，然后加入33.6克氢氧化钾(0.6 mol)，撤去冰水浴，室温反应6小时，将反应混合溶液倒入水中，剧烈搅拌20分钟，分批次用氯仿将产物萃取，萃取液用饱和氯化钠水溶液洗后旋蒸除去氯仿，浓缩液精馏收集65℃/0.23mmHg组分得产物84克，收率80％。常压沸点246～256℃，氢谱表征(1H NMR，300MHz,CDCl3,δin ppm):7.51～7.53(d,2H),7.11～7.13(d,2H)；氟谱表征(19F NMR，282MHz,CDCl3,δinppm):-86.2,(dt,2F)-68.2(dt,2F)。
实施例3中间体2:4-(1,2,2-三氟乙烯氧基)-1-溴苯的制备
Figure PCTCN2015073718-appb-000020
氩气保护下，在反应瓶中加入实施例2获得的76克4-(2-溴-1,1,2,2-四氟乙氧 基)-1-溴苯(0.22 mol)，480毫升新蒸乙腈，搅拌稀释，加入30克锌粉(0.5 mol)，升温回流反应24小时。将反应液倒入600毫升水中，搅拌15分钟以上，分批次用氯仿萃取，合并氯仿萃取液，用饱和氯化钠水溶液洗涤，无水硫酸钠干燥12小时以上。旋蒸除去氯仿，浓缩液精馏收集56.2℃/0.6mmHg组分得产物43.8克，收率61％。产物常压沸点为242～252℃，氢谱表征(1H NMR，300MHz,CDCl3,δinppm):7.47～7.49(d,2H),6.99～7.01(d,2H)；氟谱表征(19F NMR，282MHz,CDCl3,δin ppm):-134.2～-134.7(dd,1F),-126.4～-125.8(dd,1F),-119.4～-119.0(dd,1F)。
实施例4单体4-(1,2,2-三氟乙烯氧基)-1-(甲基二乙氧基硅基)-苯的制备
Figure PCTCN2015073718-appb-000021
氩气保护下，在反应瓶中加入64.2克甲基三乙氧基硅烷(0.36 mol)和200毫升新蒸四氢呋喃，搅拌稀释，加入15克镁屑，室温下剧烈搅拌，逐滴加入31克实施例3获得的中间体24-(1,2,2-三氟乙烯氧基)-1-溴苯，加完后继续在室温下搅拌反应24小时。旋蒸除去四氢呋喃和过量的甲基三乙氧基硅烷，浓缩液精馏收集62.7℃/0.6mmHg组分得产物23克，收率59％。产物常压沸点为258～262℃，氢谱表征(1H NMR，300MHz,CDCl3,δin ppm):7.64～7.66(d,2H),7.10～7.12(d,2H),3.79～3.82(q,4H),1.22～1.25(t,6H),0.35(s,3H)；氟谱表征(19F NMR，282MHz,CDCl3,δin ppm):-133.8～-134.2(dd,1F),-126.2～-126.7(dd,1F),-119.4～-119.9(dd,1F)；碳谱表征(13C NMR，75MHz,CDCl3,δin ppm):156.7,136.1,131.5,129.7,115.2,111.4,58.3,18.0,-4.4。
实施例5预聚体聚甲基-(1,2,2-三氟乙烯氧基苯基)硅氧烷的制备
氩气保护下，在反应瓶中加入72 mL甲苯，36 mL水，12 mL乙酸(0.21 mol)，13.8克由实施例4获得的单体4-(甲基二乙氧基硅基)-(1,2,2-三氟乙烯氧基)苯(45mmol)，先在室温下搅拌4小时，再在85℃下熟化5小时。分液、水洗至中性，旋蒸除去溶剂，定量获得产物。氢谱表征(1H NMR，300MHz,CDCl3,δin ppm): 7.62～7.69(m,2H),7.08～7.19(m,2H),3.78～3.88(m,4H),1.21～1.29(m,6H)，0.22～0.61(m,3H)；氟谱表征(19F NMR，282MHz,CDCl3,δin ppm):-134.1～-133.5(m,1F),-125.6～-126.4(m,1F),-119.1～-119.6(m,1F)。
实施例6预聚体聚甲基-(1,2,2-三氟乙烯氧基苯基)硅氧烷的制备
氩气保护下，在反应瓶中加入36 mL甲苯，18mL水，3 mL浓盐酸(0.25 mol)，6.9克由实施例4制备的4-(甲基二乙氧基硅基)-(1,2,2-三氟乙烯氧基)苯(22.5mmol)，先在室温下搅拌4小时，再在85℃下熟化5小时。分液、水洗至中性，旋蒸除去溶剂，定量获得产物。氢谱表征(1H NMR，300MHz,CDCl3,δin ppm):7.62～7.69(m,2H),7.08～7.19(m,2H),3.78～3.88(m,4H),1.21～1.29(m,6H)，0.22～0.61(m,3H)；氟谱表征(19F NMR，282MHz,CDCl3,δin ppm):-134.1～-133.5(m,1F),-125.6～-126.4(m,1F),-119.1～-119.6(m,1F)。
实施例7预聚体聚甲基-(1,2,2-三氟乙烯氧基苯基)硅氧烷的旋涂制膜和固化
取实施例6所获预聚物0.5克，溶于15毫升甲苯中，获得的溶液用2微米滤膜过滤后，于室温下，在转速为1000～4000 rpm下滴到严格清洗过的重掺杂硅片上(电阻率2×10-3Ω.cm)。如此采用旋涂法获得表面平整的薄膜后，将其置于氮气保护的管式炉中，先在150℃下除溶剂3小时，然后升温至180℃保持18小时或250℃下保持4小时。如此获得固化薄膜。
实施例8聚合物的耐热、介电性能和力学性能
将实施例7所制得厚度为170纳米的聚合物薄膜放入到真空干燥箱中，于200℃加热2小时，在氮气氛中冷至室温后，于薄膜表面蒸镀直径为1 mm的铝电极，并于硅片的背面蒸镀200纳米厚度的金属铝，如此获得标准薄膜电容器。通过测试薄膜电容器的电容，计算出薄膜的介电常数和介电损耗因子。
将上述通过旋涂方式获得的薄膜捣碎，置于热重分析仪中，以10℃/分钟的升温速率，测试聚合物的热分解温度和残炭量。
将上述通过旋涂方式获得的薄膜以纳米综合力学系统作纳米力学测试，得纳米硬度、杨氏模量和结合强度。
具体数据如下表所示：
Figure PCTCN2015073718-appb-000022
实施例9聚合物作为印刷电路板绝缘树脂的用途
取实施例6所获预聚物50克，溶于200毫升甲苯中，于室温下，用毛刷将溶液刷涂到预先用硅烷偶联剂KH550处理的无碱玻璃布上(600 g/m2)，于120℃下除溶剂3小时后，得到的玻璃纤维预浸料叠层(4层)，然后置于平板硫化仪中，于20Kg/cm2的压力和180℃温度下压制成型。成型后的玻璃纤维板在250℃下保持4小时得到固化的玻璃纤维复合材料，可直接用于制造印刷电路板。
所获得的玻璃纤维板吸水率0.12％，在电工设备的工作频率(50Hz)下的介电常数为2.8，介电损耗角正切4×10-3，低于目前工业上所使用的、由环氧及聚酰亚胺等为基体树脂制备的玻璃纤维增强复合材料。
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. 一种如式I所示的聚合物：
    Figure PCTCN2015073718-appb-100001
    式中，n≥2；较佳地，n＝5～100；更佳地，n＝10～20。
  2. 如权利要求1所述的式I聚合物的制备方法，其特征在于，包括步骤：
    在惰性溶剂中，用如下式II所示的含三氟乙烯基醚单元的有机硅单体进行水解聚合反应，得到式I聚合物；
    Figure PCTCN2015073718-appb-100002
    其中，R选自下组：C1-C4烷基；n的定义如权利要求1中所述；
    较佳地，所述的水解聚合反应酸性催化剂和/或水存在下进行。
  3. 一种如下式II所示的有机硅单体：
    Figure PCTCN2015073718-appb-100003
    其中，R选自下组：C1-C4烷基。
  4. 如权利要求3所述的有机硅单体的制备方法，其特征在于，通过下述步骤制备：
    (1)在极性非质子性溶剂中，在碱性催化剂存在下，用对卤代苯酚与四氟二 溴乙烷于室温下反应，制备4-(2-溴-1,1,2,2-四氟乙氧基)-1-卤代苯；
    Figure PCTCN2015073718-appb-100004
    (2)在极性非质子性溶剂中，将所述的4-(2-溴-1,1,2,2-四氟乙氧基)-1-1-卤代苯进行消去反应，得到4-(1,2,2-三氟乙烯氧基)-1-卤代苯；
    Figure PCTCN2015073718-appb-100005
    (3)在极性非质子性溶剂中，用甲基三烷氧基硅烷与4-(1,2,2-三氟乙烯氧基)-1-卤代苯反应，得到如式II所示的有机硅单体；
    Figure PCTCN2015073718-appb-100006
    上述各式中，X为卤素；R选自下组：C1-C4烷基。
  5. 如权利要求1所述的式I聚合物的用途，其特征在于，用于进行加热固化，从而制备固化聚合物。
  6. 一种聚合物，其特征在于，所述的聚合物是用如式I所述的聚合物进行固化制备的。
  7. 如权利要求6所述的聚合物的制备方法，其特征在于，所述聚合物通过以下方法制备：加热如式I所示的聚合物，从而得到如权利要求6所述的聚合物。
  8. 如权利要求7所述的方法，其特征在于，所述加热的温度范围为150～250℃。
  9. 一种制品，其特征在于，所述制品含有如权利要求1所述的式I聚合物或如权利要求6所述的聚合物，或所述制品是用如权利要求1所述的式I聚合物或如权利要求6所述的聚合物制备的。
  10. 如权利要求9所述的制品，其特征在于，所述的制品为含有权利要求6所述的聚合物的片材或薄膜，且所述的制品是通过以下方法制备的：
    用权利要求1所述的式I聚合物进行室温模压得到含有式I聚合物的片材；或用有机溶剂溶解所述式I聚合物并进行成膜，得到含有式I聚合物的薄膜；
    对上述聚合物片材或聚合物膜进行加热固化，得到含有如权利要求6所述的聚合物的片材或薄膜。
PCT/CN2015/073718 2014-03-06 2015-03-05 含六氟环丁基醚和有机硅氧烷的低介电常数聚合物及其制备和应用 WO2015131839A1 (zh)

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CN105461744B (zh) * 2014-09-12 2018-04-06 中国科学院上海高等研究院 一种含氟萘乙基有机硅单体及其制备方法和用途
CN105418926B (zh) * 2014-09-12 2018-07-13 中国科学院上海高等研究院 一种含氟萘乙基硅树脂及其制备方法和应用
CN104448320B (zh) * 2014-11-20 2017-11-07 中国科学院上海有机化学研究所 一种含三氟乙烯氧基苯基硅树脂的制造方法和应用
CN106831361B (zh) * 2015-12-04 2019-06-25 中昊晨光化工研究院有限公司 一种二卤代三氟乙烷制备三氟乙烯基芳醚类化合物的方法
CN105837617B (zh) * 2016-04-20 2019-03-15 中国科学院上海有机化学研究所 可直接热固化的含三氟乙烯基醚的环硅氧烷的制备及应用
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