CN114805660B - Synthesis of functionalized trifluoro vinyl compound and preparation method of resin thereof - Google Patents

Synthesis of functionalized trifluoro vinyl compound and preparation method of resin thereof Download PDF

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CN114805660B
CN114805660B CN202210490301.1A CN202210490301A CN114805660B CN 114805660 B CN114805660 B CN 114805660B CN 202210490301 A CN202210490301 A CN 202210490301A CN 114805660 B CN114805660 B CN 114805660B
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CN114805660A (en
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符文鑫
孙泉
李孟璐
袁紫薇
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Abstract

The invention discloses a method for synthesizing and curing two post-crosslinkable trifluoro vinyl resin monomers. The structural formula of the trifluoro vinyl resin monomer is shown as formula III and formula IV, wherein R in the formula III and the formula IV 1 And R is 2 Which may be represented as benzocyclobutene, mono-functional siloxane, di-functional siloxane, tri-functional siloxane, etc., respectively. The material obtained after curing has excellent thermal stability and mechanical properties, the dielectric properties such as dielectric constant and dielectric loss are low, and the regulation and control of the mechanical properties and the dielectric properties can be realized through the types of functional groups of side chains; the cured fluorine-containing main chain resin material can be applied to the fields of ultra-large scale integrated circuit multi-chip modules, high polymer film waveguides, wafer level chip scale packages, micro motor systems, liquid crystal display packages, signal insulation component packages and the like.

Description

Synthesis of functionalized trifluoro vinyl compound and preparation method of resin thereof
Technical Field
The invention belongs to the field of high-performance electronic packaging resin, and particularly relates to a series of synthesis and curing methods of a trifluoro vinyl resin monomer capable of being post-crosslinked.
Background
With the rapid development of 5G communication networks, there is a need for an interlayer dielectric material with high performance, low dielectric constant (k < 2.5), low dielectric loss for use in high speed communication devices. In order to meet the dielectric performance requirements of terminal electronic devices in the field of high-frequency and high-speed signal transmission networks in the future, the preparation of polymer materials with low dielectric constants and low dielectric losses has become a research hot spot in the field. Conventionally, as an interlayer dielectric material, an inorganic substance is generally used, and an organic polymer material generally has a lower dielectric constant, excellent mechanical properties and processability, as compared with an inorganic low dielectric material. The polytetrafluoroethylene molecular structure is composed of all fluorocarbon atoms, the fluorocarbon bonds in the molecular structure are the highest in bond energy in all chemical bonds, and the breaking requires larger energy, so that the polytetrafluoroethylene molecular structure has high thermal stability; the polytetrafluoroethylene has a spiral structure in the crystalline state, and has high kneading flexibility; the fluorine atom can cover the main chain of the carbon-carbon bond, and the fluorine atom shell protects the carbon-atom chain which is easy to erode, so that the polytetrafluoroethylene has excellent chemical corrosion resistance, and the fluorine atom shell also has extremely strong hydrophobicity; polytetrafluoroethylene has extremely strong fluorocarbon bonds, the molecules have no polarity, and the molecular structure is a linear polymer which is completely symmetrical and has no branched chains, so that the dielectric constant of the polytetrafluoroethylene is the lowest dielectric constant (k-2) in the currently known nonporous polymer materials.
However, the defect is also remarkable, and the polytetrafluoroethylene resin is coated by fluorine atoms, so that the polytetrafluoroethylene material has poor surface energy, and has non-stick properties with other substances, especially poor adhesion with metal materials. The polytetrafluoroethylene melt has high viscosity, and even if the heating temperature is raised to the melting point, the polytetrafluoroethylene melt cannot flow, so that the processability of the material is poor. The coefficient of thermal expansion of the polytetrafluoroethylene resin is larger, and the linear expansion coefficient of the polytetrafluoroethylene resin changes irregularly along with the change of temperature. Polytetrafluoroethylene resins have extremely high static electricity and are not allowed for many applications. One polytetrafluoroethylene material evaluated in Michael (Morgen Morgen, annu. Rev. Mater. Sci 2000,30.) laboratory was found to have a low yield stress (12 MPa), a low elastic modulus (0.5 GPa), a low softening temperature (-250 ℃) and a high Coefficient of Thermal Expansion (CTE) (> 100 ppm/. Degree.C). Together, these factors can cause the film to warp or pucker during process integration.
Aiming at the defects of polytetrafluoroethylene resin, two types of post-crosslinkable trifluoro vinyl resin monomers are introduced into the polytetrafluoroethylene resin, so that the obtained resin can retain a fluorocarbon main chain of polytetrafluoroethylene, and other properties of the resin can be regulated through a side chain capable of being post-crosslinked, and the resin material can better meet the higher requirements of the dielectric layer material in the future high-frequency communication technology.
Disclosure of Invention
The invention aims to provide a synthesis method of a functionalized trifluoro vinyl compound and a preparation method of the functionalized trifluoro vinyl compound and tetrafluoroethylene copolymer resin.
In a first aspect of the invention, there is provided a polymer of formula I wherein y, z are not simultaneously 0:
Figure BDA0003631449660000021
wherein R is 1 And R is 2 The same or different, are each independently selected from any one of the following groups: benzocyclobutenyl, mono-functionalized siloxane groups, di-functionalized siloxane groups, tri-functionalized siloxane groups;
the functional group of the siloxane group may be selected from any of the following groups: methyl, methoxy, ethyl, propyl, isopropyl, n-butyl, isobutyl, octyl, octadecyl, cyclohexyl, phenyl, trifluoromethyl, perfluorohexyl, perfluorooctyl, vinyl.
When x=z=0, formula i is a homopolymer represented by the following formula iii, and when x=y=0, formula i is a homopolymer represented by the following formula iv.
When x, y, z is not equal to 0, the formula I is a copolymer of three monomers, x, y, z is not less than 1, preferably x, y, z=1 to 200, more preferably x, y, z=30 to 120;
in another preferred embodiment, the polymer has one or more characteristics selected from the group consisting of:
the number average molecular weight of the polymer is 5000-100000;
the weight average molecular weight of the polymer is 12000-350000;
the dispersity of the polymer is 1.2-1.5.
The glass transition temperature of the polymer is 245-260 DEG C
The dielectric constant of the polymer is 2.0-2.2.
The dielectric loss factor of the polymer is 6x10 -4 ～8x10 -4 ；
The polymer has a 5% thermal weight loss temperature in nitrogen of 400-500 ℃.
The 5% thermal weight loss temperature of the polymer in the air is 350-450 ℃.
The carbon residue rate of the polymer at 1000 ℃ in nitrogen is 55% -65%.
In a second aspect of the invention there is provided a process for the preparation of a polymer as described in the first aspect of the invention.
The preparation method of the polymer shown in the formula I provided by the invention comprises the following steps:
in an inert solvent, under the action of an initiator, carrying out copolymerization on a compound of a formula II, a compound of a formula III and a compound of a formula IV to obtain a polymer shown in a formula I;
Figure BDA0003631449660000031
r in the compound of formula III 1 Is defined as in formula I, formula IV in which R 2 Is defined as in formula I.
In another preferred embodiment, the initiator may be selected from at least one of the following: perfluoroperoxides, perfluoroacyl peroxides, dihydrocarbyl peroxides. Preferably, the perfluorinated peroxides perform best, such as [ (CF) 3 ) 2 CFC(O)O] 2 。
In another preferred embodiment, the inert solvent is selected from at least one of the following: 1,2 trifluorotrichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.
In another preferred embodiment, in the reaction, the molar ratio of the reactants is: tetrafluoroethylene, compound of formula III, compound of formula IV and initiator= (0-1): (0-5): (0.05-0.1), but the dosages of the compounds of formula III and IV are not 0 at the same time.
In another preferred embodiment, the polymerization temperature is 50℃to 110 DEG C
In another preferred embodiment, the polymerization time is 5 to 24 hours.
In another preferred embodiment, the reaction is carried out under inert gas protection; preferably, the inert gas is nitrogen.
In another preferred embodiment, the reaction is carried out at a temperature of 50℃to 65℃for 24 hours or at 110℃for 5 to 8 hours.
In another preferred embodiment, after the reaction is completed, the following post-treatments of the product are also required:
(i) The copolymerization mixture (semitransparent viscous liquid) was poured into a flask, the solvent was evaporated, and the residue was heated under vacuum at 100℃overnight to give a white copolymer powder.
In another preferred embodiment, the post-processing further comprises the steps of:
(ii) Dissolving the white solid with dichloro to obtain a dichloromethane solution of the white solid;
(iii) Dropping the solution into methanol to obtain white solid, and filtering the solid to obtain the purified product.
In a third aspect of the present invention, there is provided a compound of formula III and a process for preparing the same.
Figure BDA0003631449660000032
Figure BDA0003631449660000041
In the formula III, R 1 Is defined as in formula I.
A process for the preparation of a compound of formula iii comprising the steps of: in an inert solvent, under the action of a catalyst, carrying out a root-shore reaction on a compound shown in a formula IIIa and a compound shown in a formula IIIb, namely, refluxing in the inert solvent to obtain a solution of the compound shown in the formula III.
Figure BDA0003631449660000042
Wherein, X in the compounds shown in the formulas IIIa and IIIb is defined as halogen (such as I, br and Cl); r in IIIb 1 R in formula I 1 。
When R is 1 In the case of benzocyclobutene:
in another preferred embodiment, the catalyst used in the reaction is selected from at least one of the following: tetraphenylphosphine palladium, palladium chloride, ferrocene palladium dichloride and palladium acetate. Preferably, the palladium tetraphenyl phosphine is the most cost effective.
In another preferred embodiment, the inert solvent is selected from the group consisting of: n-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide.
In another preferred embodiment, the reaction is carried out at a temperature of 100℃to 140℃and preferably at 110 ℃. In another preferred embodiment, the reaction time is 8 to 12 hours.
In another preferred example, the material formula IIIa and formula IIIb and the catalyst are fed in a molar ratio of: 1 (1-1.5) and 0.05-0.1).
The above method further comprises the following purification steps: pouring the solution containing the compound shown in the formula III into ice water solution, adding toluene to extract an organic phase, washing the organic phase with deionized water, removing water by using anhydrous magnesium sulfate, concentrating, and performing column chromatography.
When R is 1 In the case of siloxanes:
in another preferred embodiment, the catalyst used in the reaction is magnesium.
In another preferred embodiment, the inert solvent is selected from the group consisting of: anhydrous tetrahydrofuran, anhydrous diethyl ether, and the like.
In another preferred embodiment, the reaction is carried out at 60℃to 120℃under oil bath reflux, preferably at 75 ℃.
In another preferred embodiment, the reaction time is from 4 to 12 hours.
In another preferred example, the material formula IIIa and IIIb and the catalyst have the following feed ratios: 1 (1-1.5) and 1-1.5).
The above method further comprises the following purification steps: the catalyst was quenched with dilute hydrochloric acid, extracted 3 times with n-hexane, washed 3 times with saturated brine, dried over anhydrous magnesium sulfate, filtered and spin-dried.
In a fourth aspect of the invention, there is provided a compound of formula IV and a process for its preparation.
Figure BDA0003631449660000051
In the formula IV, R 2 Is defined as in formula I.
In another preferred embodiment, the compound of formula iv is synthesized by four steps of boric acid esterification, hydroxylation, etherification and reduction elimination, according to the following method:
Figure BDA0003631449660000052
wherein R in the formulas IVa, IVb, IVc and IVd 2 Is defined as in formula I;
x in the formula IVa is halogen (such as I, br and Cl).
The preparation method of the compound shown in the formula IV comprises the following steps:
boric acid esterification is carried out on the compound shown in the formula IVa and the bippinacol borate in an inert solvent to obtain a compound shown in the formula IVb; carrying out hydroxylation reaction on the formula IVb and m-chloroxylenes to obtain a formula IVc; etherification reaction is carried out on the formula IVc and 1,2 dibromotetrafluoroethane, so as to obtain a formula IVd; and (3) carrying out reduction elimination reaction on the zinc powder and the compound shown in the formula IV.
The above method further comprises the following purification steps: pouring the solution containing the compounds shown in the formulas IVa, IVb, IVc, IVd and IV into saturated saline solution, adding the dichloromethane solution to extract an organic phase, washing the organic phase with deionized water, removing water by using anhydrous magnesium sulfate, concentrating, and performing column chromatography.
In another preferred embodiment, the inert solvent is selected from the group consisting of: dimethyl sulfoxide, N, N-dimethylformamide, deionized water, ethanol and acetonitrile.
In another preferred embodiment, the catalyst used in the reaction is selected from at least one of the following: tetraphenylphosphine palladium, palladium chloride, ferrocene palladium dichloride and palladium acetate.
In another preferred embodiment, the molar ratio of compound substrate to catalyst is 1:0.05 to 0.1.
In another preferred embodiment, the reflux temperature of the reaction is between 0℃and 110 ℃.
In another preferred embodiment, the reaction time is between 8 and 24 hours.
In a fifth aspect of the invention there is provided the use of a polymer of formula i according to the first aspect of the invention as an encapsulating material or as an interlayer insulating material.
In a sixth aspect of the invention, there is provided an article comprising a polymer according to the first aspect of the invention, or prepared from a polymer according to the first aspect of the invention; preferably, the article is or comprises a polymer sheet or film according to the first aspect of the invention.
In a seventh aspect of the invention there is provided a method of making an article according to the sixth aspect of the invention, the method comprising the steps of; forming a polymer of formula i into a sheet or film by a method selected from the group consisting of: heating for molding, solution spin coating, or solution drop coating;
preferably, the solution spin coating or solution drop coating comprises the steps of: the polymer of formula I is dissolved in an organic solvent to prepare a solution.
In another preferred embodiment, the organic solvent is toluene, xylene, trimethylbenzene, diphenyl ether, cyclohexanone, chloroform, acetone, N dimethylformamide, N dimethylacetamide, one, dimethylsulfoxide, N-methylpyrrolidone, or a combination thereof.
In another preferred embodiment, the method further comprises the step of heating the sheet or film.
In another preferred embodiment, the heating temperature is 55 to 300 ℃.
In another preferred embodiment, the heating temperature is 1 to 8 hours.
Compared with the prior art, the invention has the main advantages that:
(1) The invention provides two methods for synthesizing and curing a trifluoro vinyl resin monomer capable of being post-crosslinked. The polymer of the formula I has good processability and can be used for preparing packaging materials and interlayer insulating materials. The polymer has very excellent film forming property, and the prepared organic film has good hydrophobicity and a contact angle to water of up to 120 degrees. The polymer also shows high thermal stability and low dielectric constant, and is suitable for being used as packaging materials and laminating matrix resins of electronic components in the electronic and electric industries.
(2) Compared with the prior art, the compounds of the formula III and the formula IV have a trifluoro vinyl structure, can be subjected to thermal dimerization to form a four-ring structure and can also be subjected to free radical polymerization to form a chain linear structure, and the space spiral state of the chain structure is favorable for reducing the dielectric property of the polymer material.
It is to be understood that within the scope of the present invention, new or preferred embodiments may be constructed by combining the above-described technical features of the present invention with each other and the technical features specifically described below. And are limited to a space, and are not described in detail herein.
Detailed Description
The inventors of the present invention have prepared two novel polyfluoro polymers containing structural units of trifluoroethylene or trifluoroethylene ether compounds. The polymer has good processability, heat resistance and dielectric property. Based on the above findings, the inventors have completed the present invention.
Polyfluoropolyarylether and polyfluoropolyether containing trifluoroethylene and trifluorovinyl ether structural units
It is noted that the dielectric constant of polytetrafluoroethylene is the lowest of the dielectric constants (k-2) in the presently known nonporous polymer materials. But its flexibility and uncrosslinked chain structure limit the thermo-mechanical stability of the material. Such as polytetrafluoroethylene materials, have low yield stress (12 MPa), low elastic modulus (0.5 GPa), low softening temperature (250 ℃) and high Coefficient of Thermal Expansion (CTE) (> 100ppm/°c). In view of the excellent dielectric properties of polytetrafluoroethylene, the present invention contemplates novel polyfluoro polymers containing both tetrafluoroethylene units and post-crosslinkable functional groups, aryl or alkyl groups. The polymer can be used as a high-performance coating and packaging material with good dielectric property and heat-resistant mechanical property, and is applied to the fields of microelectronics industry and aerospace.
Specifically, the invention provides a polymer shown as the following formula I, wherein y and z are not 0 at the same time:
Figure BDA0003631449660000071
wherein when x=z=0, formula i is a homopolymer of formula iii, and when x=y=0, formula i is a homopolymer of formula iv. When x, y, z. Noteq.0, the formula I is a copolymer of three monomers, x, y, z. Gtoreq.1, preferably x, y, z=1 to 120.
The polyfluoro polymer may be prepared by the following process:
in an inert solvent, under the action of an initiator, a compound of a formula II, a compound of a formula III and a compound of a formula IV react to obtain a polymer of a formula I;
Figure BDA0003631449660000072
the initiator may be selected from the group consisting of: perfluoroperoxides, perfluoroacyl peroxides, dihydrocarbyl peroxides. Preferably, the effect of the perfluoroperoxide is the best.
The inert solvent is selected from the group consisting of: 1,2 trifluorotrichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.
In the reaction, the molar ratio of the reactants is as follows: tetrafluoroethylene: trifluoroethyl compound: trifluoro vinyl ether compound: initiator=0 to 1:0 to 5:0 to 5:0.05 to 0.1. However, the amounts of formula III and formula IV are not 0 at the same time.
The reaction temperature and time of the reaction are not particularly limited, and may be adjusted according to the reaction system (e.g., solvent system or catalyst ligand, etc.). The polymerization temperature is in the range of 50-150 ℃.
The polymerization reaction temperature is 8-24 h.
In the reaction formula, each starting material can be obtained by a conventional route, for example, in a preferred example of the present invention, the compound of formula iii (trifluorovinyl compound) is synthesized as follows:
reacting with a compound of formula IIIa in an inert solvent to obtain a compound of formula III;
Figure BDA0003631449660000081
in another preferred embodiment of the present invention, the compound of formula IV (trifluorovinyl ether compound) is synthesized as follows:
the compound of the formula IVa is synthesized by four steps of reactions of boric acid esterification, hydroxylation, etherification and reduction elimination according to the following method:
Figure BDA0003631449660000082
in a solvent, carrying out boric acid esterification reaction on a formula IVa and bippinacol borate, carrying out hydroxylation reaction on a formula IVb and m-chloroxylene, carrying out etherification reaction on a formula IVc and 1,2 dibromotetrafluoroethane, and carrying out reduction elimination reaction on a formula IVd and zinc powder to obtain a formula IV;
a process for preparing a trifluoroethylene ether compound molecule of formula iv comprising the steps of: in an inert solvent, under the action of a catalyst, a reaction substrate is put into a reaction system, and reflux is carried out at different temperatures to obtain corresponding compound solutions, and the corresponding compound solutions are purified to obtain the compounds shown in the formulas IVa, IVb, IVc, IVd and IV.
The above method further comprises the following purification steps: pouring the solution containing the compounds shown in the formulas IVa, IVb, IVc, IVd and IV into saturated saline solution, adding the dichloromethane solution to extract an organic phase, washing the organic phase with deionized water, removing water by using anhydrous magnesium sulfate, concentrating, and performing column chromatography.
In another preferred embodiment, the inert solvent is selected from the group consisting of: dimethyl sulfoxide, N, N-dimethylformamide, deionized water, ethanol and acetonitrile.
In another preferred embodiment, the catalyst used in the reaction is selected from the group consisting of: tetraphenylphosphine palladium, palladium chloride, ferrocene palladium dichloride and palladium acetate.
In another preferred embodiment, the molar ratio of compound substrate to catalyst is 1:0.05 to 0.1.
In another preferred embodiment, the reflux temperature of the reaction is between 0℃and 110 ℃.
In another preferred embodiment, the reaction time is between 8 and 24 hours.
The polymers of formula i have good electrical and chemical resistance properties, for example, in preferred embodiments of the invention, the polymers have one or more characteristics selected from the group consisting of:
the number average molecular weight of the polymer is 5000-100000;
the weight average molecular weight of the polymer is 12000-350000;
the dispersity of the polymer is 1.2-1.5.
The glass transition temperature of the polymer is 245-260 DEG C
The dielectric constant of the polymer is 2.0-2.2.
The dielectric loss factor of the polymer is 6x10 -4 ～8x10 -4 ；
The polymer has a 5% thermal weight loss temperature in nitrogen of 400-500 ℃.
The 5% thermal weight loss temperature of the polymer in the air is 350-450 ℃.
The carbon residue rate of the polymer at 1000 ℃ in nitrogen is 55-65 percent
The polymer may be used as an encapsulation material or as an interlayer insulating dielectric material. For example, in a preferred embodiment of the invention, the polymers may be used to prepare interlayer dielectrics, or encapsulation materials in the microelectronics field.
Preparation of articles containing polymers of formula I
The invention also provides an article comprising the polymer of formula I, or the article is prepared from the polymer of formula I.
Preferably, the article is a sheet or film made from the polymer of formula I, or the article contains a sheet or film made from the polymer of formula I. For example, one preferred article is a metal wire having an outer surface coated with a film formed from the polymer of formula I.
The film or sheet may be prepared by the following method:
forming a polymer of formula i into a sheet or film by a method selected from the group consisting of: heating for molding, solution spin coating, or solution drop coating;
preferably, the solution spin coating or solution drop coating comprises the steps of: the polymerization of formula I is carried out, for example, by dissolving in an organic solvent, to prepare a solution.
In another preferred embodiment, the method further comprises the steps of: heating the sheet or film.
In another preferred embodiment, the heating temperature is 50 to 300 ℃.
In another preferred embodiment, the heating time is 8 to 24 hours.
In another preferred embodiment, the dielectric constant (5 GHz) of the article is in the range of 2.0 to 2.2.
In another preferred embodiment, the dielectric dissipation factor (5 GHz) of the article is 6x10 -4 ～8x10 -4 。
The polymer of the formula I has better solution processability, and is dissolved in an organic solvent for processing. The organic solvent is not particularly limited, and in a preferred example of the present invention, the organic solvent is toluene, xylene, trimethylbenzene, methylene chloride, chloroform, acetone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, or a combination thereof.
In a preferred embodiment of the invention, the article may be prepared by:
providing a substrate; and forming a film on the substrate by the method to obtain the product.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples, in which specific conditions are not noted, are generally performed under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated.
Example 1, formula IIIc (R 1 Synthesis of trifluorovinylbenzocyclobutene shown as =benzocyclobutenyl
Figure BDA0003631449660000101
1.56g of zinc powder was weighed into a 50ml three-necked flask, cooled to room temperature with oxygen removal, and then added with 20ml of an ultra-dry DMF solution, and the system was placed in an ice bath at 0 ℃. To the three-necked flask, 1.056g of iodotrifluoroethylene was added dropwise. After the completion of the dropwise addition, the ice bath was removed to room temperature and stirring was continued, 0.577g of tetraphenylphosphine palladium was added, 1.82g of 4-bromoBCB was injected, and the system temperature was raised to 110 ℃. The system was stopped after 2 hours of reaction.
After the reaction was completed, the solution was poured into 50ml of an ice water solution, and toluene was added thereto to extract an organic phase by liquid separation. After the extraction was completed, the organic phase was extracted with deionized water. And after the extraction is finished, adding anhydrous magnesium sulfate for dewatering, and carrying out column chromatography separation after rotary evaporation and concentration to obtain colorless transparent liquid. The yield was 80%.
The structure validation data are shown below:
1 H NMR(300MHz,CDCl 3 )：δ(ppm)7.34(s,H),7.25(s,H),6.92(s,H),3.17(m,2H),3.10(m,2H).
19 F NMR(500MHz,CDCl 3 ):δ(ppm):-101.41(dd,1F)，-116.1(dd,1F)，-174.1(dd1F).
EXAMPLE 2 precursor 4-borate benzocyclobutene of formula IV (formulas IVb, R 2 Benzocyclobutenyl) was taken out of a 100ml three-necked flask from an oven at 120 ℃, cooled at room temperature and used. Weighing bippinacol borate (8.3906 g), 4Br-BCB (5.4639 g) and potassium acetate (8.8338 g) into a three-necked flask, injecting 20ml of ultra-dry DMSO into the three-necked flask, bubbling at room temperature for deoxidization, and adding [1,1' -bis (diphenylphosphino) ferrocene after the bubbling is finished]0.6578g of palladium dichloride catalyst. The reaction temperature was 80 ℃.
After the reaction, the catalyst was filtered off and extracted with saturated brine and petroleum ether. And after the extraction is finished, adding anhydrous magnesium sulfate for dewatering, and carrying out column chromatography separation after rotary evaporation and concentration to obtain colorless transparent liquid. The yield was 85%.
1 H NMR(300MHz,CDCl 3 )δ7.70(s,H),7.49(s,H),7.08(s,H),3.19(s,4H),1.34.(s,12H)
EXAMPLE 3 precursor 4-hydroxybenzocyclobutene of formula IV (formula IVc, R 2 =benzocyclobutenyl) synthesis
Deionized water and ethanol were added to a 100ml round bottom flask at room temperature. Water: alcohol = 1:2, v/v. Bubbling deoxygenated, and after completion 4-borate benzocyclobutene (4.384 g) and m-CPBA (3.945 g) were added. Stirring at room temperature for 24 hr, adding 0.1M NaHCO after the experiment 3 50ml of aqueous solution. The extract was separated from ethyl acetate and saturated brine. Anhydrous magnesium sulfate was added to remove water, and column chromatography was performed after concentration by rotary evaporation to obtain 2.487g of a yellow oily product. The yield was 80%.
1 H NMR(300MHz,CDCl 3 )δ11.11(s,H),6.89(s,H),6.65(s,H),6.61(s,H),3.10(s,4H).
Example 4 etherification of 4-hydroxybenzocyclobutene precursor of formula IV (formula IVd, R 2 Benzocyclobutenyl =
Taking 50ml of three-port bottles out of a 120 ℃ drying box, cooling to room temperature, adding 1.445g of cesium carbonate, extracting 5ml of ultra-dry DMSO, adding into 4-hydroxy-BCB, uniformly mixing, extracting mixed liquid, injecting into the three-port bottles, dissolving cesium carbonate at room temperature, extracting 1.589g of 1.2 dibromotetrafluoroethane, injecting into a system, heating in an oil bath at 55 ℃ after injection, and reacting for 24 hours. The extract was separated from the aqueous solution by methylene chloride and saturated brine. Adding anhydrous magnesium sulfate for dewatering, and carrying out column chromatography separation after rotary evaporation and concentration.
1 H NMR(300MHz,CDCl 3 )δ7.26(s,H),7.05(s,H),6.96(s,H),3.17(s,4H).
19 F NMR(500MHz,CDCl 3 ):δ(ppm):-67.9(s,2F)，-85.84(s，2F).
Example 5 Synthesis of benzocyclobutene of the trifluoroethylene Ether of formula IV
Under the protection of nitrogen, adding 6.5g of activated zinc powder and 50ml of ultra-dry acetonitrile into a dry 100ml three-port bottle, placing the system into an oil bath pot at 90 ℃, dropwise adding raw materials into a stirred zinc powder acetonitrile suspension through a syringe pump, heating and refluxing for 16h, separating liquid and extracting after the reaction is finished, combining organic phases, dehydrating through anhydrous magnesium sulfate, concentrating and steaming in a rotary manner, and separating by column chromatography. The compound was obtained as a colorless liquid.
1 H NMR(300MHz,CDCl 3 )δ7.00(s,H),6.94(s,H),6.84(s,H),3.13(s,4H).
19 F NMR(500MHz,CDCl 3 )δ-120.44(dd,1F),-127.44(dd,1F),-133.31(dd,1F).
Example 6 prepolymerization Ia of formula IIIc (formula I, z=0)
Figure BDA0003631449660000111
/>
Figure BDA0003631449660000121
Comprises 1, 2-trifluorotrichloroethane F-113 (23 ml) and a perfluoro initiator [ (CF) 3 ) 2 CFC(O)O] 2 Added to a 50ml stainless steel reactor, stirred, cooled to-196 ℃ and the internal air was vented, then the temperature was raised to room temperature, and reciprocated three times to remove air. Two monomers were mixed according to a molar ratio of 1:1 are introduced into the reactor via vacuum lines, respectively, and the reactor is then slowly brought to room temperature, shaken and heated to 55℃for 24 hours.
The copolymerization mixture (semitransparent viscous liquid) was introduced into a flask, the solvent was evaporated, and the residue was dried under vacuum at 100 ℃ to give a white copolymer powder. The yield was 77.2%.
EXAMPLE 7 prepolymerization Ib of formula IIIc (formula I, y=0)
Figure BDA0003631449660000122
Comprises 1, 2-trifluorotrichloroethane F-113 (23 ml) and a perfluoro initiator [ (CF) 3 ) 2 CFC(O)O] 2 Added to a 50ml stainless steel reactor, stirred, cooled to-196 ℃ and the internal air was vented, then the temperature was raised to room temperature, and reciprocated three times to remove air. Two monomers were mixed according to a molar ratio of 1:1 are introduced into the reactor via vacuum lines, respectively, and the reactor is then slowly brought to room temperature, shaken and heated to 55℃for 24 hours.
The copolymerization mixture (semitransparent viscous liquid) was introduced into a flask, the solvent was evaporated, and the residue was dried under vacuum at 100 ℃ to give a white copolymer powder. Yield 78.2%.
Example 8 prepolymerization of formula IIIc (formula I, x=0) formula ic
Figure BDA0003631449660000123
Comprises 1, 2-trifluorotrichloroethane F-113 (23 ml) and a perfluoro initiator [ (CF) 3 ) 2 CFC(O)O] 2 Added to a 50ml stainless steel reactor, stirred, cooled to-196 ℃ and the internal air was vented, then the temperature was raised to room temperature, and reciprocated three times to remove air. Two monomers were mixed according to a molar ratio of 1:1 are introduced into the reactor via vacuum lines, respectively, and the reactor is then slowly brought to room temperature, shaken and heated to 55℃for 24 hours.
The copolymerization mixture (semitransparent viscous liquid) was introduced into a flask, the solvent was evaporated, and the residue was dried under vacuum at 100 ℃ to give a white copolymer powder. The yield was 80.1%.
EXAMPLE 9 prepolymerization of formula Id
Figure BDA0003631449660000131
Comprises 1, 2-trifluorotrichloroethane F-113 (23 ml) and a perfluoro initiator [ (CF) 3 ) 2 CFC(O)O] 2 Added to a 50ml stainless steel reactor, stirred, cooled to-196 ℃ and the internal air was vented, then the temperature was raised to room temperature, and reciprocated three times to remove air. Three monomers were mixed in a molar ratio of 1:1:1 are introduced into the reactor via vacuum lines, respectively, and the reactor is then slowly brought to room temperature, shaken and heated to 55℃for 24 hours.
The copolymerization mixture (semitransparent viscous liquid) was introduced into a flask, the solvent was evaporated, and the residue was dried under vacuum at 100 ℃ to give a white copolymer powder. Weight average molecular weight 2.3X10 4 Pdi=2.2, yield 79%. The polymer has a molecular weight of about 125000 and a dispersity of 1.5.
EXAMPLE 10 trifunctional siloxane precursor of formula IIId (R in formula III 1 =trimethylOxy-silyl) preparation
Figure BDA0003631449660000132
Activated magnesium chips (38 mmol) and 2 iodine simple substances are added into a three-mouth bottle, nitrogen is pumped three times, more than ten drops of ultra-dry THF solution of iodine trifluoroethylene are dripped, the blower is heated to initiate reaction, dripping is continued, the dripping speed is controlled, and the dripping is completed approximately 1 hour. Reflux at 70 ℃, TLC monitored the reaction, 1h of reaction complete, and the system was cooled to room temperature.
Trimethoxychlorosilane (38 mmol) was weighed out from the glove box, dissolved in ultra-dry THF, added dropwise to the above grignard reagent for 30min, and the in-bottle solution changed from silver gray to pale yellow. The flask was refluxed at 75deg.C with an oil bath, and after 4 hours the heating was stopped and the pale yellow solution in the flask was removed. Extracting with n-hexane for 3 times, washing with saturated saline water for 3 times, drying with anhydrous magnesium sulfate, filtering, and spin-drying. A colorless liquid was obtained in 80.6% yield.
EXAMPLE 11 prepolymerization of trifunctional siloxanes of formula IIId
Figure BDA0003631449660000133
Comprises 1, 2-trifluorotrichloroethane F-113 (23 ml) and a perfluoro initiator [ (CF) 3 ) 2 CFC(O)O] 2 Added to a 50ml stainless steel reactor, stirred, cooled to-196 ℃ and the internal air was vented, then the temperature was raised to room temperature, and reciprocated three times to remove air. Two monomers were mixed according to a molar ratio of 1:1 are introduced into the reactor via vacuum lines, respectively, and the reactor is then slowly brought to room temperature, shaken and heated to 55℃for 24 hours.
The copolymerization mixture (semitransparent viscous liquid) was introduced into a flask, the solvent was evaporated, and the residue was dried under vacuum at 100 ℃ to give a white copolymer powder. Weight average molecular weight 3.1X10 4 Pdi=2.5, yield 77.2%. The polymer was found to have a molecular weight of about 89500 and a dispersity of 1.4.
EXAMPLE 12 preparation of monofunctional siloxane precursor of formula IIIe (R in formula III 1 Methoxy dimethylsilyl group =
Figure BDA0003631449660000141
Activated magnesium chips (38 mmol) and 2 iodine simple substances are added into a three-mouth bottle, nitrogen is pumped three times, more than ten drops of ultra-dry THF solution of iodine trifluoroethylene are dripped, the blower is heated to initiate reaction, dripping is continued, the dripping speed is controlled, and the dripping is completed approximately 1 hour. Reflux at 70 ℃, TLC monitored the reaction, 1h of reaction complete, and the system was cooled to room temperature.
Monomethoxy dimethylchlorosilane (38 mmol) was weighed from the glove box, dissolved in ultra-dry THF, added dropwise to the above grignard reagent for 30min, and the in-bottle solution changed from silver gray to pale yellow. The flask was refluxed at 75deg.C with an oil bath, and after 4 hours the heating was stopped and the pale yellow solution in the flask was removed. Extracting with n-hexane for 3 times, washing with saturated saline water for 3 times, drying with anhydrous magnesium sulfate, filtering, and spin-drying. A colorless liquid was obtained in 82.6% yield.
EXAMPLE 13 Pre-polymerization of monofunctional siloxanes of formula IIIe
Figure BDA0003631449660000142
Comprises 1, 2-trifluorotrichloroethane F-113 (23 ml) and a perfluoro initiator [ (CF 3) 2CFC (O)] 2 Added to a 50ml stainless steel reactor, stirred, cooled to-196 ℃ and the internal air was vented, then the temperature was raised to room temperature, and reciprocated three times to remove air. Two monomers were mixed according to a molar ratio of 1:1 are introduced into the reactor via vacuum lines, respectively, and the reactor is then slowly brought to room temperature, shaken and heated to 55℃for 24 hours.
The copolymerization mixture (semitransparent viscous liquid) was introduced into a flask, the solvent was evaporated, and the residue was dried under vacuum at 100 ℃ to give a white copolymer powder. Weight average molecular weight 3.5X10 4 ，PDi=2.6, yield 70.2%. The measured molecular weight of the polymer was about 89800 and the dispersity was 1.4.
EXAMPLE 14 preparation of difunctional siloxane precursor of formula IIIf (R in formula III 1 Methyl dimethoxy silane group =
Figure BDA0003631449660000151
Activated magnesium chips (38 mmol) and 2 iodine simple substances are added into a three-mouth bottle, nitrogen is pumped three times, more than ten drops of ultra-dry THF solution of iodine trifluoroethylene are dripped, the blower is heated to initiate reaction, dripping is continued, the dripping speed is controlled, and the dripping is completed approximately 1 hour. Reflux at 70 ℃, TLC monitored the reaction, 1h of reaction complete, and the system was cooled to room temperature.
Monomethoxy dimethylchlorosilane (38 mmol) was weighed from the glove box, dissolved in ultra-dry THF, added dropwise to the above grignard reagent for 30min, and the in-bottle solution changed from silver gray to pale yellow. The flask was refluxed at 75deg.C with an oil bath, and after 4 hours the heating was stopped and the pale yellow solution in the flask was removed. Extracting with n-hexane for 3 times, washing with saturated saline water for 3 times, drying with anhydrous magnesium sulfate, filtering, and spin-drying. A colorless liquid was obtained in 82.6% yield.
EXAMPLE 15 preparation of difunctional siloxanes of the formula IIIf
Figure BDA0003631449660000152
Comprises 1, 2-trifluorotrichloroethane F-113 (23 ml) and a perfluoro initiator [ (CF 3) 2 CFC(O)O] 2 Added to a 50ml stainless steel reactor, stirred, cooled to-196 ℃ and the internal air was vented, then the temperature was raised to room temperature, and reciprocated three times to remove air. Two monomers were mixed according to a molar ratio of 1:1 are introduced into the reactor via vacuum lines, respectively, and the reactor is then slowly brought to room temperature, shaken and heated to 55℃for 24 hours.
Introducing the copolymerization mixture (semitransparent viscous liquid) into a flask, evaporating solvent, and collecting residueThe residue was dried under vacuum at 100℃to give a white copolymer powder. Weight average molecular weight 2.1X10 4 Pdi=3.0, yield 69.5%. The polymer has a molecular weight of about 58600 and a dispersity of 1.5.
EXAMPLE 16 curing of benzocyclobutene-containing side chain Pre-Polymer
0.5g of the prepolymer obtained in the formulae Ia, ib, ic and Id was dissolved in 5ml of trimethylbenzene, and the obtained solution was spin-coated on a heavily doped silicon wafer, and then placed in a vacuum oven and heated at 200℃for 2 hours. After cooling, an aluminum electrode having a diameter of 1mm was vapor-deposited on the film surface, and aluminum metal having a thickness of 200nm was vapor-deposited on the back surface of the silicon wafer, thus obtaining standard film capacitors Pa, pb, pc and Pd. The dielectric constant and dielectric dissipation factor of the film were calculated by testing the capacitance of the film capacitor.
EXAMPLE 17 curing of a prepolymer containing siloxane side chains
0.5g of the prepolymer obtained in the formulae IIId, IIIe and IIIf was dissolved in 25ml of tetrahydrofuran, and 0.1ml of deionized water and 0.4ml of 0.01M diluted hydrochloric acid were added thereto and stirred at room temperature for 8 to 24 hours. After the experiment, the organic phase is extracted by liquid separation, the viscous liquid is spin-coated on a heavily doped silicon wafer, and then the silicon wafer is placed into a vacuum drying oven and heated for 8 hours at 60 ℃. After cooling, aluminum electrodes having a diameter of 1mm were vapor-deposited on the film surface, and metal aluminum having a thickness of 200nm was vapor-deposited on the back surface of the silicon wafer, thus obtaining standard film capacitors Pe, pf and Pg. The dielectric constant and dielectric dissipation factor of the film were calculated by testing the capacitance of the film capacitor. The results are shown in Table 1 below.
TABLE 1
Figure BDA0003631449660000161
All documents mentioned in this application are incorporated by reference as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the claims appended hereto.

Claims (15)

1. A polymer of formula i:
Figure FDA0004210414260000011
R 1 and R is 2 The same or different, are each independently selected from any one of the following groups: benzocyclobutenyl, mono-functionalized siloxane groups, di-functionalized siloxane groups, tri-functionalized siloxane groups;
the functional group of the siloxane is selected from any one of the following groups: methyl, methoxy, ethyl, propyl, isopropyl, n-butyl, isobutyl, octyl, octadecyl, cyclohexyl, phenyl, trifluoromethyl, perfluorohexyl, perfluorooctyl, vinyl;
in the x, y and z, x, y and z are not less than 0, but y and z are not 0 at the same time.
2. The polymer of claim 1, wherein: the x, y and z are more than or equal to 1;
the number average molecular weight of the polymer is 5000-100000;
or, the weight average molecular weight of the polymer is 12000-350000.
3. The polymer of claim 2, wherein: the x, y, z=1 to 200.
4. A polymer according to claim 3, wherein: the x, y, z=3 to 120.
5. A process for the preparation of a polymer of formula i as claimed in any one of claims 1 to 4, comprising the steps of:
in an inert solvent, under the action of an initiator, carrying out copolymerization on a compound of a formula II, a compound of a formula III and a compound of a formula IV to obtain a polymer of a formula I;
Figure FDA0004210414260000012
r in the compound of formula III 1 Is defined as in formula I, formula IV in which R 2 Is defined as in formula I.
6. The method of manufacturing according to claim 5, wherein: the initiator is selected from at least one of the following: perfluoroperoxides, perfluoroacyl peroxides, and dihydrocarbyl peroxides;
the inert solvent is selected from at least one of the following: 1,2 trifluoro trichloroethane, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide;
in the reaction, the mol ratio of the reactants is tetrafluoroethylene to formula III to formula IV to initiator= (0-1) to (0-5) to (0.05-0.1);
the temperature of the polymerization reaction is 50-110 ℃; the polymerization reaction time is 5-24 hours;
the reaction is carried out under the protection of inert gas.
7. The method of manufacturing according to claim 6, wherein: the initiator is perfluoro peroxide;
the inert gas is nitrogen.
8. The preparation method according to any one of claims 5 to 7, characterized in that: the preparation method of the compound shown in the formula III comprises the following steps: in an inert solvent, under the action of a catalyst, carrying out a root-base reaction on a compound shown in a formula IIIa and a compound shown in a formula IIIb to obtain a solution of the compound shown in the formula III;
Figure FDA0004210414260000021
wherein X in the compounds shown in the formulas IIIa and IIIb is defined as halogen; r in the compound shown in the formula IIIb 1 R in formula III 1 ；
When R is 1 In the case of benzocyclobutene:
the catalyst used in the reaction is at least one selected from the following: tetraphenylphosphine palladium, palladium chloride, ferrocene palladium dichloride, palladium acetate;
the inert solvent is selected from the group consisting of: n-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide;
the reaction is carried out at 100-140 ℃;
the reaction time is 8-12 h;
the feeding mole ratio of the formula IIIa to the formula IIIb and the catalyst is as follows: 1 (1-1.5) 0.05-0.1);
when R is 1 In the case of siloxanes:
the catalyst used in the reaction is magnesium;
the inert solvent is selected from the group consisting of: anhydrous tetrahydrofuran, anhydrous diethyl ether;
the reaction is carried out in an oil bath reflux state at 60-120 ℃; the reaction time is 4-12h;
the feeding mole ratio of the formula IIIa to the formula IIIb and the catalyst is as follows: 1 (1-1.5) and 1-1.5).
9. The method of preparing as claimed in claim 8, wherein: the reaction was carried out at 75℃under reflux in an oil bath.
10. The production method according to any one of claims 5 to 7, characterized in that: the preparation method of the compound shown in the formula IV comprises the following steps:
boric acid esterification is carried out on the compound shown in the formula IVa and the bippinacol borate in an inert solvent to obtain a compound shown in the formula IVb; carrying out hydroxylation reaction on the formula IVb and m-chloroxylenes to obtain a formula IVc; carrying out etherification reaction on the formula IVc and 1,2 dibromotetrafluoroethane to obtain a formula IVd; carrying out reduction elimination reaction on the zinc powder and the compound shown in the formula IV;
Figure FDA0004210414260000031
wherein R in the formulas IVa, IVb, IVc and IVd 2 Is defined as in formula I;
x in the formula IVa is halogen.
11. Use of a polymer according to any of claims 1-4 as an encapsulation material or as an interlayer insulation material.
12. An article comprising the polymer of any one of claims 1-4 or prepared from the polymer of any one of claims 1-4.
13. The article of manufacture of claim 12, wherein: the article is a sheet or film of the polymer of any one of claims 1-4, or the article comprises a sheet or film of the polymer of any one of claims 1-4.
14. A method of preparing an article according to claim 12 or 13, characterized in that the method comprises the steps of: forming a polymer of formula i into a sheet or film by a method selected from the group consisting of: heating for molding, solution spin coating, or solution drop coating.
15. The method of manufacturing according to claim 14, wherein: the solution spin coating or solution drop coating comprises the following steps: the polymer of formula I is dissolved in an organic solvent to prepare a solution.
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