CN103865066B - Low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as preparation and application of low-dielectric-constant polymer - Google Patents

Low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as preparation and application of low-dielectric-constant polymer Download PDF

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CN103865066B
CN103865066B CN201410081245.1A CN201410081245A CN103865066B CN 103865066 B CN103865066 B CN 103865066B CN 201410081245 A CN201410081245 A CN 201410081245A CN 103865066 B CN103865066 B CN 103865066B
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polymer
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dielectric
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CN103865066A (en
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房强
袁超
金凯凯
刁屾
王佳佳
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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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 System
    • 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

Abstract

The invention relates to a low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as a preparation and application of the low-dielectric-constant polymer and particularly provides a polymer prepared by heating and curing a polymer represented by a formula I as well as a preparation method and an application of the polymer. The polymer has good electrical properties and heat resistance, is simple in preparation method and is applied to an encapsulating material taken as an insulation coating layer and an electronic component in electronic and electrical industries.

Description

Low dielectric constant polymer and its preparation of the ether of cyclobutyl containing hexafluoro and organosiloxane And application
Technical field
The invention belongs to high-performance polymer manufacturing technology field, in particular it relates to a kind of excellent in mechanical performance, The ether of cyclobutyl containing hexafluoro and the low dielectric constant polymer of siloxanes of low water absorption and low-k, and preparation method thereof and Using.
Background technology
Traditionally, the interlayer dielectric materials in integrated circuit adopt silicon dioxide or silicone-based materials.These materials Although with very high heat stability and thermomechanical property, its dielectric constant is often higher than 3.0, it is impossible to meet high frequency communications The requirement of equipment.Polyimide-type materials are good because of thermostability, by pore-creating, it is possible to obtain the relatively low thin film of dielectric constant, make It is widely used for the succedaneum of silicon dioxide.However, the glass transition temperature of common polyimides often below collects Into the processing temperature of circuit board, and the material easily carries out ordered arrangement along metal or silicon face in film forming procedure, so that Polyimides dielectric materials have anisotropy, including each to different of conduction of heat, resistant to shearing intensity and dielectric properties Property.Therefore, industrial department and institute further developed many organic polymer species dielectric materials.But, these materials Expect that usual heat stability is not enough, it is poor with the surface adhesiveness of metal or silicon.With the development of microelectronics industry, based on copper-connection skill The manufacturing industry of 90 nano chips of art proposes many demands, above-described pure siliceous and organic polymer to material industry The situation being gradually eliminated will be faced.The most pressing problem faced by people is that needs are developed There is the material of high thermostability again.
Poly- hexafluoro cyclobutyl arylene ethers material has excellent thermostability and photoelectric properties because of which, from the nineties in 20th century Rise, people are just studied to which.So far, due to higher efficiency of transmission and minimum light loss, they by Fully be developed as organic light-guide material (referring to Macromolecules2004,37,5724 and Macromolecules2005, 38,8278).On the other hand, because C-F keys have less polarizable rate, with three-functionality-degree ether structure containing trifluoro vinyl it is Performed polymer, prepares the thermosetting resin that main chain contains hexafluoro cyclobutyl arylene ether functional group by hot setting and has been developed that simultaneously As advanced low-k materials (see Mat.Res.Soc.Symp.Proc.1997,443,177).In recent years, come from tetrafluoroethene Freon C318 base aryl ether (polyperfluorocyclobutane, PFCB) birds of the same feather flock together compound by people pay much attention to, Reason is, this kind of polymer not only advantage of lower cost, and with excellent electric property and low hydroscopicity (see WO9015043).But, the heat stability and adhesive property for being based entirely on the organic framework structured dielectric materials of PFCB is not enough. Therefore, it is necessary to be devoted to improving and eliminating these defects.
The content of the invention
It is an object of the invention to provide the PFCB of a kind of heat stability and adhesive property improvement organic framework structured low Jie Electric material.
A kind of a first aspect of the present invention, there is provided polymer shown in formula I：
In formula, n >=2；It is preferred that n=5～100；More preferably, n=10～20.
In another preference, described Formulas I polymer is liquid, preferably colourless thick liquid.
In another preference, the number-average molecular weight of the polymer is 2,300～4,600.
In another preference, the weight average molecular weight of the polymer is 4,300～8,600.
In another preference, described Formulas I polymer can be heating and curing, it is preferred that described Formulas I polymer is consolidated It is 150 DEG C～250 DEG C to change temperature.
A kind of a second aspect of the present invention, there is provided preparation method of Formulas I polymer as described in the first aspect of the invention, Methods described includes step：In atent solvent, with the organic silicon monomer containing trifluoro vinyl ether unit as shown in Formula Il Be hydrolyzed polyreaction, obtains Formulas I polymer；
Wherein, R is selected from the group：C1-C4 alkyl；N is as defined above described in text.
In another preference, described hydrolytic-polymeric reaction is carried out in the solvent being selected from the group：Benzene, toluene, diformazan Benzene, or its combination.
In another preference, the reaction temperature of described hydrolytic-polymeric reaction is 0-100 DEG C.
In another preference, the described hydrolytic-polymeric reaction time is 5～36 hours.
In another preference, the described hydrolytic-polymeric reaction time is 12～36 hours.
In another preference, carry out in the presence of described hydrolytic-polymeric reaction acidic catalyst and/or water.
In another preference, described acidic catalyst is selected from the group：Hydrochloric acid, sulphuric acid, acetic acid, formic acid, or its combination.
Organosilicon list in another preference, in described hydrolytic-polymeric reaction, shown in water, acidic catalyst and Formula II The mol ratio of body is 50～100：1～10:1～10.
In another preference, the organic silicon monomer shown in described Formula II is prepared by following step：
(1) in polar aprotic solvent, in the presence of base catalyst, with to halogenated phenol and dibromotetrafluoromethane React at room temperature, prepare 4- (bromo- 1,1,2, the 2- tetrafluoro ethyoxyls of 2-) -1- halogeno-benzenes；
(2) in polar aprotic solvent, by described 4- (bromo- 1,1,2, the 2- tetrafluoro ethyoxyls of 2-) -1-1- halos Benzene carries out elimination reaction, obtains 4- (1,2,2- trifluoro-ethylene epoxide) -1- halogeno-benzenes；
(3) in polar aprotic solvent, with methyl trialkoxysilane and 4- (1,2,2- trifluoro-ethylene epoxide) -1- Halogeno-benzene reacts, and obtains the organic silicon monomer as shown in Formula II；
It is above-mentioned it is various in, X is halogen；R is selected from the group：C1-C4 alkyl.
In another preference, in the step (1), described base catalyst is selected from the group：Potassium carbonate, hydroxide Potassium, or its combination.
In another preference, in the step (1), described polar aprotic solvent is selected from the group：N- methyl Ketopyrrolidine, DMSO, or its combination.
In another preference, in the step (1), described is selected from the group to halogenated phenol：P bromophenol, to chlorine Phenol, or its combination.
In another preference, in the step (1), the described response time is 5～30 hours.
It is in another preference, in the step (1), described to halogenated phenol and the mol ratio of dibromotetrafluoromethane For 1:1～10.
In another preference, in the step (2), described polar aprotic solvent is acetonitrile.
In another preference, in the step (2), described elimination reaction is being carried out in the presence of zinc powder.
In another preference, in the step (2), the described response time is 5～30 hours.
In another preference, in the step (2), described 4- (bromo- 1,1,2, the 2- tetrafluoro ethyoxyls of 2-) -1-1- The mol ratio of halogeno-benzene and zinc powder is 1：1～5.
In another preference, in the step (3), described polar aprotic solvent is selected from the group：Tetrahydrochysene furan Mutter, ether, or its combination.
In another preference, in the step (3), described reaction is carried out in the presence of magnesium chips.
In another preference, in the step (3), described alkoxyl is the alkoxyl of C1-C4, it is preferred that institute The alkoxyl stated is selected from the group：Methoxy or ethoxy.
In another preference, in the step (3), described 4- (1,2,2- trifluoro-ethylene epoxide) -1- halogeno-benzenes Add in the following manner：It is formulated as Deca after tetrahydrofuran solution.
In another preference, in the step (3), the described response time is 12～36 hours.
In another preference, in the step (3), described reaction temperature is 0-50 DEG C.
A third aspect of the present invention, there is provided a kind of Formulas I polymer as described in the first aspect of the invention is used to carry out adding Heat cure, so as to prepare the purposes of solidification polymer.
In another preference, described is heating and curing temperature for 150 DEG C～250 DEG C.
A kind of a fourth aspect of the present invention, there is provided polymer, described polymer are entered with the polymer as described in Formulas I It is prepared by row solidification：It is preferred that described be cured as being heating and curing.
In another preference, described polymer is with the structure as shown in formula III：
In formula, m is positive integer, and m≤n.
In another preference, described polymer (final cured product) Si-PFCB is the network structure of crosslinking.
In another preference, described polymer has one or more following feature：
The dielectric constant of the polymer is≤2.5, preferably≤2.4 (determining under 30MHz)；
In a nitrogen atmosphere, 5% heat decomposition temperature of the polymer is >=450 DEG C, preferably >=470 DEG C；
The hardness of the polymer is >=0.35GPa, preferably >=0.38GPa；
The Young's moduluss of the polymer are >=8.00GPa, preferably >=9.00GPa, are more preferably >=10.00GPa；
The bond strength of the polymer and silicon chip is >=4.5GPa, preferably >=4.8GPa, more preferably for >= 4.90GPa。
A fifth aspect of the present invention, there is provided a kind of preparation method of the polymer as described in fourth aspect present invention, institute State polymer to be prepared by the following method：Heating polymer shown in formula I, so as to obtain as described in fourth aspect present invention Polymer.
In another preference, the temperature range of the heating is 150～250 DEG C.
A sixth aspect of the present invention, there is provided a kind of product, the product contain Formulas I as described in the first aspect of the invention Polymer or the polymer as described in fourth aspect present invention, or the product is the Formulas I with as described in the first aspect of the invention Prepared by polymer or the polymer as described in fourth aspect present invention.
In another preference, described product is selected from the group：Advanced low-k materials, plain conductor outer cladding insulation material Material, polymer sheet, thin polymer film.
In another preference, described product is attached most importance to the polymer thin of doped silicon wafer-as described in fourth aspect present invention Film.
In another preference, described product is that glass fibre-polymer as described in fourth aspect present invention is combined Material.
In another preference, described product is printed circuit board (PCB).
In another preference, described product is the polymer sheet containing the polymer described in fourth aspect present invention Or thin polymer film, and described product is prepared by the following method：
Room temperature molding is carried out with the Formulas I polymer described in first aspect present invention and obtains the sheet material containing Formulas I polymer；Or The Formulas I polymer is dissolved with organic solvent and film forming is carried out, the film containing Formulas I polymer is obtained；
Above-mentioned polymer sheet or polymeric film are heating and curing, are obtained containing as described in fourth aspect present invention The polymer sheet or thin polymer film of polymer.
In another preference, described film-forming process is spin-coating film or drop coating film forming.
In another preference, described organic solvent is toluene, dimethylbenzene, trimethylbenzene, diphenyl ether, Ketohexamethylene, trichlorine Methane, acetone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide, N-Methyl pyrrolidone, or its group Close.
A kind of a seventh aspect of the present invention, there is provided organic silicon monomer as shown in Formula Il：
Wherein, R is selected from the group：C1-C4 alkyl.
A kind of a eighth aspect of the present invention, there is provided preparation side of the organic silicon monomer as described in seventh aspect present invention Method, is prepared by following step：
(1) in polar aprotic solvent, in the presence of base catalyst, with to halogenated phenol and dibromotetrafluoromethane React at room temperature, prepare 4- (bromo- 1,1,2, the 2- tetrafluoro ethyoxyls of 2-) -1- halogeno-benzenes；
(2) in polar aprotic solvent, by described 4- (bromo- 1,1,2, the 2- tetrafluoro ethyoxyls of 2-) -1-1- halos Benzene carries out elimination reaction, obtains 4- (1,2,2- trifluoro-ethylene epoxide) -1- halogeno-benzenes；
(3) in polar aprotic solvent, with methyl trialkoxysilane and 4- (1,2,2- trifluoro-ethylene epoxide) -1- Halogeno-benzene reacts, and obtains the organic silicon monomer as shown in Formula II；
It is above-mentioned it is various in, X is halogen；R is selected from the group：C1-C4 alkyl.
In another preference, in the step (1), described base catalyst is selected from the group：Potassium carbonate, hydroxide Potassium, or its combination.
In another preference, in the step (1), described polar aprotic solvent is selected from the group：N- methyl Ketopyrrolidine, DMSO, or its combination.
In another preference, in the step (1), described is selected from the group to halogenated phenol：P bromophenol, to chlorine Phenol, or its combination.
In another preference, in the step (1), the described response time is 5～30 hours.
It is in another preference, in the step (1), described to halogenated phenol and the mol ratio of dibromotetrafluoromethane For 1:1～10.
In another preference, in the step (2), described polar aprotic solvent is acetonitrile.
In another preference, in the step (2), described elimination reaction is being carried out in the presence of zinc powder.
In another preference, in the step (2), the described response time is 5～30 hours.
In another preference, in the step (2), described 4- (bromo- 1,1,2, the 2- tetrafluoro ethyoxyls of 2-) -1-1- The mol ratio of halogeno-benzene and zinc powder is 1：1～5.
In another preference, in the step (3), described polar aprotic solvent is selected from the group：Tetrahydrochysene furan Mutter, ether, or its combination.
In another preference, in the step (3), described reaction is carried out in the presence of magnesium chips.
In another preference, in the step (3), described alkoxyl is the alkoxyl of C1-C4, it is preferred that institute The alkoxyl stated is selected from the group：Methoxy or ethoxy.
In another preference, in the step (3), described 4- (1,2,2- trifluoro-ethylene epoxide) -1- halogeno-benzenes Add in the following manner：It is formulated as Deca after tetrahydrofuran solution.
In another preference, in the step (3), the described response time is 12～36 hours.
In another preference, in the step (3), described reaction temperature is 0-50 DEG C.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and have in below (eg embodiment) Can be combined with each other between each technical characteristic of body description, so as to constitute new or preferred technical scheme.As space is limited, exist This no longer tires out one by one states.
Specific embodiment
The present inventor is passed through through in-depth study discovery for a long time, the organosiloxane of the functional group of ether containing trifluoro vinyl After hydrolysis, the direct hot settings of prepolymer Jing for being obtained can obtain a kind of novel organosiloxane material of structure.Described Material has preferable electric property, heat stability and adhesive property, is suitable as a kind of high property of high heat-resisting, low-k Energy coating and encapsulating material, are applied to the fields such as microelectronics industry, Aero-Space and national defence.Based on above-mentioned discovery, inventor is complete Into the present invention.
Term
As used herein, term " cured product of Formula II polymer ", the Si-PFCB polymer of the present invention " " or " six are contained The low dielectric constant polymer of fluorine cyclobutyl ether and organosiloxane " refers both to be heating and curing with the Formula II polymer of the present invention Prepared polymer, a kind of preferred structure is as shown in formula III：
Unless stated otherwise, term " halo " refers to that one or more hydrogen atoms on group are replaced by halogen atom, its In, described halogen atom is selected from the group：Fluorine, chlorine, bromine, iodine.
Term " C1-C4 alkyl " refers to the straight or branched alkyl with 1～4 carbon atom, for example methyl, ethyl, propyl group, Isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group or similar group.
Term " C1-C4 alkoxyls " refers to the straight or branched alkoxyl with 1-4 carbon atom, such as methoxyl group, ethoxy Base, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy or similar group.
Flucride siloxane performed polymer
The invention provides a kind of low-k that can be used for preparing the ether of cyclobutyl containing hexafluoro and organosiloxane is poly- The performed polymer of compound, described performed polymer is shown in formula I：
In formula, n >=2；It is preferred that n=5～100；More preferably, n=10～20.
In another preference, the number-average molecular weight of the polymer is 2,300～4,600.
In another preference, the weight average molecular weight of the polymer is 4,300～8,600.
In the preference of the present invention, described Formulas I polymer can be hydrolyzed to be polymerized with monomer and be prepared, for example：
In atent solvent, it is hydrolyzed with the organic silicon monomer containing trifluoro vinyl ether unit as shown in Formula Il poly- Reaction is closed, Formulas I polymer is obtained；
Wherein, R is selected from the group：C1-C4 alkyl；n≥2；It is preferred that n=5～100；More preferably, n=10～20.
In another preference, described hydrolytic-polymeric reaction is carried out in the solvent being selected from the group：Benzene, toluene, diformazan Benzene, or its combination.
The reaction temperature of described hydrolytic-polymeric reaction is not particularly limited, for example can under the reflux temperature of solvent, Or carry out under the boiling point of ROH.In the preference of the present invention, described reaction temperature is 0-100 DEG C, preferably 4-95 ℃。
In another preference, the described hydrolytic-polymeric reaction time is 5～20 hours.
Described hydrolytic-polymeric reaction can be carried out in the presence of a catalyst, for example, in a preference of the present invention, Described reaction is carried out in the presence of acidic catalyst and/or water.Wherein, described acidic catalyst includes (but being not limited to) The acid being selected from the group：Hydrochloric acid, sulphuric acid, acetic acid, formic acid, or its combination.
Organosilicon list in another preference, in described hydrolytic-polymeric reaction, shown in water, acidic catalyst and Formula II The mol ratio of body is 50～100：5～10:1.
Organic silicon monomer shown in described Formula II can be prepared by the conventional method of this area, for example, can be passed through It is prepared by following step：
(1) in polar aprotic solvent, in the presence of base catalyst, with to halogenated phenol and dibromotetrafluoromethane React at room temperature, prepare 4- (bromo- 1,1,2, the 2- tetrafluoro ethyoxyls of 2-) -1- halogeno-benzenes；
In another preference, in the step (1), described base catalyst is selected from the group：Potassium carbonate, hydroxide Potassium, or its combination.
In another preference, in the step (1), described polar aprotic solvent is selected from the group：N- methyl Ketopyrrolidine, DMSO, or its combination.
In another preference, in the step (1), described is selected from the group to halogenated phenol：P bromophenol, to chlorine Phenol, or its combination.
The response time of the step (1) is not particularly limited, and can determine reaction end by TLC methods, in the present invention A preference in, described response time is 10～30 hours.
It is in another preference, in the step (1), described to halogenated phenol and the mol ratio of dibromotetrafluoromethane For 1:1～10.
(2) in polar aprotic solvent, by described 4- (bromo- 1,1,2, the 2- tetrafluoro ethyoxyls of 2-) -1-1- halos Benzene carries out elimination reaction, obtains 4- (1,2,2- trifluoro-ethylene epoxide) -1- halogeno-benzenes；
Wherein, described polar aprotic solvent is not particularly limited, and can be preferably acetonitrile.
Described elimination reaction in optional catalyst condition, or can be entered under any suitable reaction condition OK, for example, can carry out under zinc powder effect.
The response time of the step (2) is not particularly limited, and can determine reaction end by TLC methods, in the present invention A preference in, described response time is 5～30 hours.
In another preference, in the step (2), described 4- (bromo- 1,1,2, the 2- tetrafluoro ethyoxyls of 2-) -1-1- The mol ratio of halogeno-benzene and zinc powder is 1：1～5.
(3) in polar aprotic solvent, with methyl trialkoxysilane and 4- (1,2,2- trifluoro-ethylene epoxide) -1- Halogeno-benzene reacts, and obtains the organic silicon monomer as shown in Formula II.
In another preference, in the step (3), described polar aprotic solvent is selected from the group：Tetrahydrochysene furan Mutter, ether, or its combination.
In another preference, in the step (3), described reaction is carried out in the presence of magnesium chips.
In another preference, in the step (3), described alkoxyl is the alkoxyl of C1-C4, it is preferred that institute The alkoxyl stated is selected from the group：Methoxy or ethoxy.
In another preference, in the step (3), described 4- (1,2,2- trifluoro-ethylene epoxide) -1- halogeno-benzenes Add in the following manner：It is formulated as Deca after tetrahydrofuran solution.
In another preference, in the step (3), the described response time is 12～36 hours.
In another preference, in the step (3), described reaction temperature is 0-50 DEG C.
In another preference, in the step (3), described 4- (bromo- 1,1,2, the 2- tetrafluoro ethyoxyls of 2-) -1-1- The mol ratio of halogeno-benzene and zinc powder is 1：1～5.
(or performed polymer) of described Formulas I polymer can be heating and curing, so as to prepare the ether of cyclobutyl containing hexafluoro and The low dielectric constant polymer of organosiloxane, a kind of preferred polymer are the polymer as shown in formula III.
The low dielectric constant polymer of the ether of cyclobutyl containing hexafluoro and organosiloxane
Good adhesion based on the high-fire resistance of organosilicon, workability and with silicon chip, and hexafluoro cyclobutyl arylene The low-dielectric energy of ether, such as combines both, and can obtain the good low-k of heat-resist, mechanical property in theory Material.The present invention is based on the present Research of above-mentioned dielectric materials, from molecular design theory, by hexafluoro cyclobutyl virtue Base ether and organosiloxane combine the heat cured material of acquisition.
Specifically, the invention provides one kind is heating and curing with above-mentioned Formulas I polymer, so as to the polymer for preparing (Si-PFCB polymer i.e. of the invention).A kind of structure of the preferred polymer is as shown in formula III：
In formula, m is positive integer, and m≤n.
In the preferred embodiment of the present invention, the Si-PFCB polymer of the present invention is the network structure of crosslinking.
In another preference, described polymer has one or more following feature：
The dielectric constant of the polymer is≤2.5, preferably≤2.4 (determining under 30MHz)；
In a nitrogen atmosphere, 5% heat decomposition temperature of the polymer is >=450 DEG C, preferably >=470 DEG C；
The hardness of the polymer is >=0.35GPa, preferably >=0.38GPa；
The Young's moduluss of the polymer are >=8.00GPa, preferably >=9.00GPa, are more preferably >=10.00GPa；
The bond strength of the polymer and silicon chip is >=4.5GPa, preferably >=4.8GPa, more preferably for >= 4.90GPa。
In the present invention, described polymer is preferably prepared by the following method：
Heating polymer shown in formula I, so as to obtain the Si-PFCB polymer of the present invention.Prepare this in aforementioned manners The Si-PFCB polymer of invention, it is simple with preparation method, the characteristics of obtained polymer performance is excellent.
The condition of the heating has no particular limits, it is preferred that being to heat at 150～250 DEG C in temperature range.
The application of the low dielectric constant polymer of the ether of cyclobutyl containing hexafluoro and organosiloxane
The polymer described in Formulas I polymer and fourth aspect present invention described in first aspect present invention can be used for preparing A series of products, in another preference, described product is selected from the group：Advanced low-k materials, plain conductor outer cladding are exhausted Edge material, polymer sheet, thin polymer film.
Wherein, the preferred product of a class is the product of the Si-PFCB polymer containing the present invention, and described product is preferred Ground is prepared by the following method：Molding is carried out with Formulas I polymer, preform is obtained, then the preform is entered Row is heating and curing, and obtains the product of the Si-PFCB polymer containing the present invention.
In a preference of the present invention, the product of the described Si-PFCB polymer containing the present invention is polymer Sheet material or thin polymer film, and described product is to be prepared by the following method
Room temperature molding is carried out with Formulas I polymer and obtains polymer sheet；Or the Formulas I polymer is dissolved simultaneously with organic solvent Carry out film forming and obtain thin polymer film, then described polymer sheet or thin polymer film are heating and curing, are contained There are the polymer sheet or thin polymer film of the Si-PFCB polymer of the present invention.
In another preference, described film-forming process is spin-coating film or drop coating film forming.
In another preference, described organic solvent is toluene, dimethylbenzene, trimethylbenzene, diphenyl ether, Ketohexamethylene, trichlorine Methane, acetone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide, N-Methyl pyrrolidone, or its group Close.
Main advantages of the present invention include：
(1) the Si-PFCB polymer that the present invention is provided has good electric property and thermostability, at one of the present invention In preference the Si-PFCB polymer of the prepared present invention have it is low up to 2.33 dielectric constant (30MHz), 5% thermal decomposition temperature Up to 471 DEG C, hardness is 0.392GPa to degree, and Young's moduluss are 10.06GPa, and the bond strength with silicon chip is 4.93GPa.
(2) dielectric materials synthesis cost provided by the present invention is relatively low, and preparation process is simple, can have as a class excellent The high performance electronic packaging material or plain conductor external coating of different heat stability, low water absorption and low-k, is applied to The field such as micro-electronic machining industry and large electric machine industry.
(3) performed polymer provided by the present invention can be used to prepare with good electric property, heat resistance and mechanical property The polymer of energy, and preparation method is simple, is adapted to industrialized production.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limit the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally according to conventional strip Part, or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage ratio and number are calculated by weight.
The preparation of 1 intermediate 14- of embodiment (the bromo- 1,1,2,2- tetrafluoros ethyoxyls of 2-) -1- bromobenzenes
Under argon protection, the bromo- phenol (0.3mol) of 51.9 grams of 4- of addition, 147 grams of 1,2- dibromo tetrafluoros in reaction unit Ethane (0.57mol) and 300 milliliters of existing DMSO (dimethyl sulfoxide) for steaming, stir 30 minutes under ice-water bath, are subsequently adding 80 grams Anhydrous potassium carbonate (0.6mol), removes ice-water bath, and reaction mixture is poured into water, is stirred vigorously 20 by room temperature reaction 6 hours Minute, product being extracted with chloroform in batches, after extract saturated sodium-chloride water solution is washed, revolving removes chloroform, concentrated solution essence Evaporate collection 65 DEG C/0.23mmHg components and obtain 98 grams of product, yield 93%.226～246 DEG C of atmospheric boiling point, hydrogen stave levy (1H NMR, 300MHz,CDCl3,δin ppm):7.51～7.53 (d, 2H), 7.11～7.13 (d, 2H);Fluorine stave levy (19F NMR, 282MHz,CDCl3,δin ppm):-86.2,(dt,2F)-68.2(dt,2F)。
The preparation of 2 intermediate 14- of embodiment (the bromo- 1,1,2,2- tetrafluoros ethyoxyls of 2-) -1- bromobenzenes
Under argon protection, the bromo- phenol (0.3mol) of 51.9 grams of 4- of addition, 147 grams of 1,2- dibromo tetrafluoros in reaction unit Ethane (0.57mol) and 300 milliliters of existing N-Methyl pyrrolidone for steaming, stir 30 minutes under ice-water bath, are subsequently adding 33.6 grams Potassium hydroxide (0.6mol), removes ice-water bath, and reaction mixture is poured into water, is stirred vigorously 20 points by room temperature reaction 6 hours Product is extracted by clock in batches with chloroform, and after extract saturated sodium-chloride water solution is washed, revolving removes chloroform, concentrated solution rectification Collect 65 DEG C/0.23mmHg components and obtain 84 grams of product, yield 80%.246～256 DEG C of atmospheric boiling point, hydrogen stave levy (1H NMR, 300MHz,CDCl3,δin ppm):7.51～7.53 (d, 2H), 7.11～7.13 (d, 2H);Fluorine stave levy (19F NMR, 282MHz,CDCl3,δin ppm):-86.2,(dt,2F)-68.2(dt,2F)。
3 intermediate 2 of embodiment:The preparation of 4- (1,2,2- trifluoro-ethylene epoxides) -1- bromobenzenes
Under argon protection, in reaction bulb, add embodiment 2 to obtain 76 grams of 4- (bromo- 1,1,2,2- tetrafluoro ethoxies of 2- Base) -1- bromobenzenes (0.22mol), 480 milliliters of new steaming acetonitriles, agitation and dilution, 30 grams of zinc powders (0.5mol) of addition, temperature rising reflux is anti- Answer 24 hours.Reactant liquor is poured in 600 milliliters of water, is stirred more than 15 minutes, in batches with chloroform extraction, merge chloroform extraction Liquid, is washed with saturated sodium-chloride water solution, anhydrous sodium sulfate drying more than 12 hours.Revolving removes chloroform, and concentrated solution rectification is received Collection 56.2 DEG C/0.6mmHg components obtain 43.8 grams of product, yield 61%.Product atmospheric boiling point be 242～252 DEG C, hydrogen stave levy (1H NMR, 300MHz, CDCl3,δin ppm):7.47～7.49 (d, 2H), 6.99～7.01 (d, 2H);Fluorine stave levy (19F NMR, 282MHz,CDCl3,δin ppm):- 134.2～-134.7 (dd, 1F), -126.4～-125.8 (dd, 1F), -119.4～- 119.0(dd,1F)。
The preparation of 4 monomer 4- of embodiment (1,2,2- trifluoro-ethylene epoxides) -1- (methyl diethoxy silicon substrate)-benzene
Under argon protection, 64.2 grams of MTESs (0.36mol) and 200 milliliters of new steamings are added in reaction bulb Tetrahydrofuran, agitation and dilution add 15 grams of magnesium chips, are stirred vigorously under room temperature, are added dropwise over the intermediate that 31 grams of embodiments 3 are obtained 24- (1,2,2- trifluoro-ethylene epoxide) -1- bromobenzenes, continue reaction 24 hours is stirred at room temperature after adding.Revolving removes tetrahydrochysene The MTES of furan and excess, concentrated solution rectification are collected 62.7 DEG C/0.6mmHg components and obtain 23 grams of product, yield 59%.Product atmospheric boiling point be 258～262 DEG C, hydrogen stave levy (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);Fluorine stave is levied (19F NMR, 282MHz, CDCl3,δin ppm):- 133.8～-134.2 (dd, 1F), -126.2～-126.7 (dd, 1F), - 119.4～-119.9 (dd, 1F)；Carbon stave levy (13C NMR, 75MHz, CDCl3,δin ppm):156.7,136.1,131.5, 129.7,115.2,111.4,58.3,18.0,-4.4。
The preparation of the poly- methyl of 5 performed polymer of embodiment-(1,2,2- trifluoro-ethylene phenyls) siloxanes
Under argon protection, addition 72mL toluene, 36mL water, 12mL acetic acid (0.21mol) in reaction bulb, 13.8 grams by reality Monomer 4- (methyl diethoxy silicon substrate)-(1,2,2- trifluoro-ethylene epoxide) benzene (45mmol) of the acquisition of example 4 is applied, first at room temperature Stirring 4 hours, then ripening 5 hours at 85 DEG C.Divide liquid, be washed to neutrality, revolving removes solvent, quantitatively obtains product.Hydrogen is composed Characterize (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);Fluorine stave levy (19F NMR, 282MHz, CDCl3,δin ppm):- 134.1～-133.5 (m, 1F), -125.6～-126.4 (m, 1F), -119.1～-119.6 (m, 1F).
The preparation of the poly- methyl of 6 performed polymer of embodiment-(1,2,2- trifluoro-ethylene phenyls) siloxanes
Under argon protection, addition 36mL toluene, 18mL water, 3mL concentrated hydrochloric acid (0.25mol) in reaction bulb, 6.9 grams by reality 4- (methyl diethoxy silicon substrate)-(1,2,2- trifluoro-ethylene epoxide) benzene (22.5mmol) of the preparation of example 4 is applied, is first stirred at room temperature Mix 4 hours, then ripening 5 hours at 85 DEG C.Divide liquid, be washed to neutrality, revolving removes solvent, quantitatively obtains product.Hydrogen stave Levy (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);Fluorine stave levy (19F NMR, 282MHz, CDCl3,δin ppm):- 134.1～-133.5 (m, 1F), -125.6～-126.4 (m, 1F), -119.1～-119.6 (m, 1F).
The spin coating masking of the poly- methyl of 7 performed polymer of embodiment-(1,2,2- trifluoro-ethylene phenyls) siloxanes and solidification
0.5 gram of 6 obtained prepolymer of Example, is dissolved in 15 milliliters of toluene, and the solution of acquisition is filtered with 2 micron membrane filters Afterwards, at room temperature, (resistivity 2 × 10 on the heavy doping silicon chip for strictly cleaning is dripped in the case where rotating speed is 1000～4000rpm-3 Ω.cm).After the thin film of surfacing is so obtained using spin-coating method, it is placed in the tube furnace of nitrogen protection, first 150 Solvent is removed 3 hours at DEG C, then heat to be kept for 4 hours at 180 DEG C of holdings 18 hours or 250 DEG C.Cured film is obtained so.
The heat-resisting of 8 polymer of embodiment, dielectric properties and mechanical property
The thin polymer film that thickness obtained by embodiment 7 is 170 nanometers is put in vacuum drying oven, is added in 200 DEG C Heat 2 hours, after being cooled to room temperature, is deposited with the aluminium electrode of a diameter of 1mm in film surface, and steams in the back side of silicon chip in blanket of nitrogen The metallic aluminium of 200 nano thickness is plated, standard thin film capacitor is so obtained.By the electric capacity of testing film capacitor, calculate The dielectric constant and dielectric loss factor of thin film.
The thin film obtained above by spin coating mode is smashed to pieces, is placed in thermogravimetric analyzer, with 10 DEG C/min of intensification speed Rate, the heat decomposition temperature and carbon left of test polymer.
The thin film obtained above by spin coating mode is made into nanometer mechanics test with nanometer synthesis mechanical system, nanometer is obtained hard Degree, Young's moduluss and bond strength.
Concrete data are as shown in the table：
Purposes of 9 polymer of embodiment as printed circuit board (PCB) insulating resin
50 grams of 6 obtained prepolymer of Example, is dissolved in 200 milliliters of toluene, at room temperature, brushes solution with hairbrush and arrive In advance with (600g/m on the alkali-free glass cloth of Silane coupling agent KH550 process2), after removing solvent 3 hours at 120 DEG C, obtain Glass fibre prepreg lamination (4 layers), be subsequently placed in compression molding instrument, in 20Kg/cm2Pressure and 180 DEG C at a temperature of It is compressing.Glass mat after molding keeps the glass fiber compound material for obtaining for 4 hours solidifying at 250 DEG C, can be straight Connect for manufacturing printed circuit board (PCB).
The glass mat water absorption rate 0.12% for being obtained, the dielectric constant under the operating frequency (50Hz) of electrical equipment For 2.8, dielectric loss angle tangent 4 × 10-3, less than it is at present industrial it is used, by setting based on epoxy and polyimides etc. Glass fibre reinforced composion prepared by fat.
The all documents referred in the present invention are all incorporated as reference in this application, independent just as each document It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned teachings for having read the present invention, those skilled in the art can To make various changes or modifications to the present invention, these equivalent form of values equally fall within the model limited by the application appended claims Enclose.

Claims (11)

1. a kind of polymer shown in formula I：
In formula, n >=2.
2. polymer as claimed in claim 1, it is characterised in that n=5～100.
3. polymer as claimed in claim 1, it is characterised in that n=10～20.
4. the preparation method of Formulas I polymer as claimed in claim 1, it is characterised in that including step：
In atent solvent, polymerization is hydrolyzed instead with the organic silicon monomer containing trifluoro vinyl ether unit as shown in Formula Il Should, obtain Formulas I polymer；
Wherein, R is selected from the group：C1-C4 alkyl；The definition of n is as described in the appended claim 1.
5. preparation method as claimed in claim 4, it is characterised in that described hydrolytic-polymeric reaction acidic catalyst and/or Carry out in the presence of water.
6. the purposes of Formulas I polymer as claimed in claim 1, it is characterised in that for being heating and curing, it is solid so as to prepare Fluidized polymer.
7. a kind of polymer, it is characterised in that described polymer be carried out with Formulas I polymer as claimed in claim 1 it is solid Change what is prepared.
8. the preparation method of polymer as claimed in claim 7, it is characterised in that the polymer is made by the following method It is standby：Formulas I polymer of the heating as shown in claim 1, so as to obtain polymer as claimed in claim 6.
9. method as claimed in claim 8, it is characterised in that the temperature range of the heating is 150～250 DEG C.
10. a kind of product, it is characterised in that the product contains Formulas I polymer as claimed in claim 1 or such as claim Polymer described in 7, or the product is with Formulas I polymer as claimed in claim 1 or as claimed in claim 7 is polymerized Prepared by thing.
11. products as claimed in claim 10, it is characterised in that described product is containing the polymerization described in claim 7 The sheet material or thin film of thing, and described product is prepared by the following method：
Room temperature molding is carried out with the Formulas I polymer described in claim 1 and obtains the sheet material containing Formulas I polymer；Or with organic molten Agent is dissolved the Formulas I polymer and carries out film forming, obtains the thin film containing Formulas I polymer；
Above-mentioned polymer sheet or polymeric film are heating and curing, are obtained containing polymer as claimed in claim 7 Sheet material or thin film.
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